Hydrophilic treatment coating composition and hydrophilizing treatment method

ABSTRACT

Provided are (1) a hydrophilic treatment coating composition containing a compound that contains a radical reactive functional group and a sulfonic acid alkali metal salt group, a radical polymerization initiator, and a polar compatibilizer, (2) a hydrophilic treatment coating composition containing a silane coupling agent that contains a radical reactive functional group, a compound that contains a radical reactive functional group and a sulfonic acid alkali metal salt group, a radical polymerization initiator, and a polar compatibilizer, (3) a hydrophilic treatment coating composition containing a compound that contains a functional group that reacts with a reactive functional group of a silane coupling agent in a surface layer, and a sulfonic acid (alkali metal salt) group, and a polar compatibilizer, and (4) a hydrophilic treatment coating composition containing a silane coupling agent that contains a reactive functional group, a compound that contains a functional group that reacts with the reactive functional group and a sulfonic acid (alkali metal salt) group, and a polar compatibilizer.

TECHNICAL FIELD

The present invention relates to a composition that is used in ahydrophilic treatment of a surface layer, which contains an inorganiccompound, of crockery, glass, metal, and the like so as to improvewashability, and a method thereof. Priority is claimed on JapanesePatent Application Nos. 2014-145541 and 2014-145542, filed on Jul. 16,2014, the contents of which are incorporated herein by reference.

BACKGROUND ART

In the related art, with respect to crockery such as a toilet bowl and awashstand which are installed at a water-using site in a building, andthe like, various kinds of surface treatments are performed to makewashing of a surface contaminant easy. Recently, in a contaminant, anoily component has been increased due to an effect of westernization ina dietary life of human beings, and thus it is difficult to sufficientlywash a contaminant from a surface of the crockery.

Although not intended to wash a surface, Patent Document 1 discloses amethod in which a surface of a material mainly containing silicon oxideis treated with a silane coupling agent, and then a reactive surfactant,which has a reactive group such as an acryloyl group or a vinyl group inthe middle of a side chain or a hydrophobic group, is allowed to reactwith the surface so as to give an anti-fog property, an antifoulingproperty, and the like to a glass product. Patent Document 1 alsodiscloses a specific compound in the method.

Patent Document 2 discloses a composition that contains a silanecoupling agent that includes an epoxy group and an isocyanate group, ahydrophilic polymer having a functional group that is allowed to reactwith the epoxy group and the isocyanate group, and a hydrophilic groupsuch as potassium sulphonate, and an alkoxide compound such astetraalkoxysilane, and the like so as to form a hydrophilic filmexcellent in the antifouling property and abrasion resistance on asurface of a base material such as a glass plate.

CITATION LIST Patent Literature

[Patent Document 1] Japanese Unexamined Patent Application, FirstPublication No. H8-259270

[Patent Document 2] Japanese Unexamined Patent Application, FirstPublication No. 2007-138104

SUMMARY OF INVENTION Technical Problem

However, in the method of using the compound disclosed in PatentDocument 1, the compound has a branched chain structure having 9 to 12carbon atoms, and thus it is difficult for hydrophilic portions toconcentrate on a surface. Therefore, there is a concern that even whenthe compound is used in the crockery such as the toilet bowl and thewashstand which are frequently subjected to washing with water,sufficient washability is not provided.

In addition, when using a compound that does not have the branchedstructure, hydrophilicity of a hydrophilic group is high, and thus thehydrophilic group is likely to be crystallized. Therefore, it isdifficult to uniformly hydrophilize the surface of the crockery and thelike.

In addition, when the composition disclosed in Patent Document 2 isformed as a film on a surface of a glass substrate and the like, aweight-average molecular weight of the hydrophilic polymer is 3000 to9900, and a main chain is long, and thus the hydrophilic group is lesslikely to concentrate on a surface. Accordingly, there is a concern thatthe hydrophilicity of a coated film is not sufficient.

Accordingly, an object of the invention is to provide a hydrophilictreatment agent and a hydrophilic treatment method which are capable ofreducing the number of washing times by preventing calcium and the likefrom being settled to crockery such as toilet bowl and a washstand,which are installed in a water-using site in a building and contains aninorganic compound such as silicon oxide, and the like, and by makingwashing off of an oily contaminant, which becomes a cause forpropagation of a fungi and an offensive odor, easy.

Solution to Problem

According to a first aspect of the invention, the following hydrophilictreatment coating compositions of [1] to [5] are provided.

[1] A hydrophilic treatment coating composition that allows a surfacelayer that contains an inorganic compound to react with a radicalreactive functional group of a silane coupling agent after a treatmentof the surface layer with a silane coupling agent that contains theradical reactive functional group. The hydrophilic treatment coatingcomposition contains: a hydrophilic compound that contains a radicalreactive functional group and an alkali metal salt of a sulfonic acidgroup, does not contain a hydrophilic portion at a site other than anend of a molecular chain, and does not contain a branched chain; aradical polymerization initiator; and a polar compatibilizer.

The hydrophilic treatment coating composition of this aspect of theinvention is a composition that hydrophilizes the surface layer thatcontains the inorganic compound after the treatment of the surface layerwith the silane coupling agent that contains the radical reactivefunctional group.

Here, specifically, the hydrophilic portion represents a nonionichydrophilic group such as ethylene oxide, a hydroxyl group, and an aminogroup, and the like.

When one end of a molecular chain of the hydrophilic compound is set asa first end, and the other end is set as a second end, the hydrophiliccompound has the radical reactive functional group at the first end ofthe molecular chain, and has the alkali metal salt of the sulfonic acidgroup at the second end of the molecular chain. The hydrophilic compounddoes not contain the hydrophilic portion at a site other than the firstend and the second end, and does not have a branched chain. That is,when the one end of the molecular chain of the hydrophilic compound isset as the first end, and the other end is set as the second end, thehydrophilic compound has the radical reactive functional group at thefirst end of the molecular chain, and has the alkali metal salt of thesulfonic acid group at the second end of the molecular chain. Thehydrophilic compound does not contain a hydrophilic portion other thanthe radical reactive functional group and the sulfonic acid group, anddoes not have the branched chain.

When the one end of the molecular chain of the hydrophilic compound isset as the first end, and the other end is set as the second end, it ispreferable that the hydrophilic compound has the radical reactivefunctional group at the first end of the molecular chain, has the alkalimetal salt of the sulfonic acid group at the second end of the molecularchain, does not contain a hydrophilic portion at a site other than thefirst end and the second end, that is, a hydrophilic portion other thanthe radical reactive functional group and the sulfonic acid group, anddoes not have a branched chain having 5 or more carbon atoms.

[2] A hydrophilic treatment coating composition that is allowed to reactwith a surface layer that contains an inorganic compound. Thehydrophilic treatment coating composition contains: a silane couplingagent that contains a radical reactive functional group; a hydrophiliccompound that contains a radical reactive functional group and an alkalimetal salt of a sulfonic acid group, does not contain a hydrophilicportion at a site other than an end of a molecular chain, and does notcontain a branched chain; a radical polymerization initiator; and apolar compatibilizer.

This composition is a composition that hydrophilizes the surface layerthat is not treated with the silane coupling agent and contains theinorganic compound.

Specifically, the hydrophilic portion represents a nonionic hydrophilicgroup such as ethylene oxide, a hydroxyl group, and an amino group, andthe like.

Here, the silane coupling agent has the radical reactive functionalgroup. When one end of a molecular chain of the hydrophilic compound isset as a first end and the other end is set as a second end, thehydrophilic compound has the radical reactive functional group at thefirst end of the molecular chain, and has the alkali metal salt of thesulfonic acid group at the second end of the molecular chain. Thehydrophilic compound does not contain the hydrophilic portion at a siteother than the first end and the second end, and does not have abranched chain.

That is, when the one end of the molecular chain of the hydrophiliccompound is set as the first end, and the other end is set as the secondend, the hydrophilic compound has the radical reactive functional groupat the first end of the molecular chain, and has the alkali metal saltof the sulfonic acid group at the second end of the molecular chain. Thehydrophilic compound does not contain a hydrophilic portion other thanthe radical reactive functional group and the sulfonic acid group, anddoes not have the branched chain.

When the one end of the molecular chain of the hydrophilic compound isset as the first end, and the other end is set as the second end, it ispreferable that the hydrophilic compound has the radical reactivefunctional group at the first end of the molecular chain, has the alkalimetal salt of the sulfonic acid group at the second end of the molecularchain, does not contain a hydrophilic portion at a site other than thefirst end and the second end, that is, a hydrophilic portion other thanthe radical reactive functional group and the sulfonic acid group, anddoes not have a branched chain having 5 or more carbon atoms.

[3] In the hydrophilic treatment coating composition according to [1] or[2], the radical reactive functional group of the hydrophilic compoundmay be at least one kind that is selected from an acrylamide group, anacryloyl group, a methacryloyl group, an allyl group, a vinyl group, astyryl group, and a mercapto group.

[4] In the hydrophilic treatment coating composition according to anyone of [1] to [3], a number-average molecular weight of the hydrophiliccompound may be 70 to 500.

[5] In the hydrophilic treatment coating composition according to anyone of [1] to [4], the compatibilizer may be at least one kind selectedfrom an amide compound, an aprotic polar solvent, polyhydric alcohol,saccharides, a polar resin, and inorganic salts.

According to a second aspect of the invention, there are provided thefollowing hydrophilic treatment methods of [6] and [7].

[6] A hydrophilic treatment method including: treating a surface layerthat contains an inorganic compound with a silane coupling agent thatcontains a radical reactive functional group; applying a hydrophilictreatment coating composition to the surface layer that is coupled withthe silane coupling agent, the hydrophilic treatment coating compositioncontaining a hydrophilic compound that contains a radical reactivefunctional group and an alkali metal salt of a sulfonic acid group, doesnot contain a hydrophilic portion at a site other than an end of amolecular chain, and does not contain a branched chain, a radicalpolymerization initiator, and a polar compatibilizer; and allowing theradical reactive functional group of the silane coupling agent and theradical reactive functional group of the hydrophilic compound to reactwith each other with a radical that occurs from the radicalpolymerization initiator due to light or heat.

Here, specifically, the hydrophilic portion represents a nonionichydrophilic group such as ethylene oxide, a hydroxyl group, and an aminogroup, and the like.

The hydrophilic compound is the same as the hydrophilic compounddescribed in [1], and is preferably an appropriate hydrophilic compounddescribed in [1].

[7] A hydrophilic treatment method including treating a surface layerthat contains an inorganic compound with a silane coupling agent thatcontains a radical reactive functional group; applying a hydrophilictreatment coating composition to the surface layer that is coupled withthe silane coupling agent, the hydrophilic treatment coating compositioncontaining a compound that contains a radical reactive functional groupand a sulfonic acid group, does not contain a hydrophilic portion at asite other than an end of a molecular chain, and does not contain abranched chain, a radical polymerization initiator, and a polarcompatibilizer; allowing the radical reactive functional group of thesilane coupling agent and the radical reactive functional group of thecompound to react with each other with a radical that occurs from theradical polymerization initiator due to light or heat; and allowing thesulfonic acid group of the compound to react with a hydroxide of analkali metal to form sulphonate.

Specifically, the hydrophilic portion represents a nonionic hydrophilicgroup such as ethylene oxide, a hydroxyl group, and an amino group, andthe like.

Here, the silane coupling agent has the radical reactive functionalgroup. In the compound that reacts with the silane coupling agent, whenone end of a molecular chain of the compound is set as a first end, andthe other end is set as a second end, the compound has the radicalreactive functional group at the first end of the molecular chain, andhas the sulfonic acid group at the second end of the molecular chain.The compound does not contain a hydrophilic portion at a site other thanthe first end and the second end, and does not have a branched chain.That is, when the one end of the molecular chain of the compound is setas the first end, and the other end is set as the second end, thecompound has the radical reactive functional group at the first end ofthe molecular chain, has the sulfonic acid group at the second end ofthe molecular chain, does not contain a hydrophilic portion other thanthe radical reactive functional group and the sulfonic acid group, anddoes not have the branched chain.

When the one end of the molecular chain of the compound is set as thefirst end, and the other end is set as the second end, it is preferablethat the compound has the radical reactive functional group at the firstend of the molecular chain, has the sulfonic acid group at the secondend of the molecular chain, does not contain a hydrophilic portion at aportion other than the first end and the second end, that is, does notcontain a hydrophilic portion other than the radical reactive functionalgroup and the sulfonic acid group, and does not have a branched chainhaving 5 or more carbon atoms.

According to a third aspect of the invention, there are provided thefollowing hydrophilic treatment coating compositions of [8] to [12].

[8] A hydrophilic treatment coating composition that allows a surfacelayer that contains an inorganic compound to react with a reactivefunctional group of a silane coupling agent after a treatment of thesurface layer with the silane coupling agent that contains at least onereactive functional group selected from an isocyanate group, an epoxygroup, an amino group, and a mercapto group. The composition contains: ahydrophilic compound which contains a functional group that is at leastone selected from an amino group, a hydroxyl group, a mercapto group,and an epoxy group, and reacts with the reactive functional group of thesilane coupling agent, and sulfonic acid or an alkali metal salt of thesulfonic acid group, and which does not contain a hydrophilic portion ata site other than an end of a molecular chain; and a polarcompatibilizer.

The composition is a composition that hydrophilizes the surface layerthat contains the inorganic compound after the treatment of the surfacelayer with the silane coupling agent having the reactive functionalgroup.

Here, the meaning of “hydrophilic portion” is the same as in descriptionof [1].

When one end of a molecular chain of the hydrophilic compound is set asa first end, and the other end of the molecular chain is set as a secondend, the hydrophilic compound has the functional group that is at leastone selected from the amino group, the hydroxyl group, the mercaptogroup, and the epoxy group, and reacts with the reactive functionalgroup of the silane coupling agent at the first end of the molecularchain, and has the sulfonic acid group or the alkali metal salt of thesulfonic acid group at the second end of the molecular chain. Thehydrophilic compound does not have a hydrophilic portion at a site otherthan the first end and the second end.

That is, when the one end of the molecular chain of the hydrophiliccompound is set as the first end, and the other end is set as the secondend, the hydrophilic compound has the functional group that reacts withthe reactive functional group of the silane coupling agent at the firstend of the molecular chain, and has the sulfonic acid group or thealkali metal salt of the sulfonic acid group at the second end of themolecular chain. The hydrophilic compound does not have a hydrophilicportion other than the functional group that reacts with the reactivefunctional group of the silane coupling agent, and the sulfonic acidgroup.

[9] A hydrophilic treatment coating composition that is allowed to reactwith a surface layer that contains an inorganic compound. Thecomposition contains: a silane coupling agent that contains (a) at leastone reactive functional group selected from an isocyanate group, anepoxy group, an amino group, and a mercapto group; (b) a hydrophiliccompound which contains a functional group that is at least one selectedfrom an amino group, a hydroxyl group, a mercapto group, and an epoxygroup, and reacts with the reactive functional group of the silanecoupling agent, and a sulfonic acid group or an alkali metal salt of thesulfonic acid group, and which does not contain a hydrophilic portion ata site other than an end of a molecular chain; and (c) a polarcompatibilizer.

This composition is a composition that hydrophilizes the surface layerthat contains the inorganic compound and is not treated with the silanecoupling agent.

Here, the meaning of the “hydrophilic portion” is the same as indescription of [1].

When one end of a molecular chain of the hydrophilic compound is set asa first end, and the other end is set as a second end, the hydrophiliccompound has the functional group that is at least one selected theamino group, the hydroxyl group, the mercapto group, and the epoxygroup, and reacts with the reactive functional group of the silanecoupling agent at the first end of the molecular chain, and has thesulfonic acid group or the alkali metal salt of the sulfonic acid groupat the second end of the molecular chain. The hydrophilic compound doesnot have a hydrophilic portion at a site other than the first end andthe second end.

That is, when the one end of the molecular chain of the hydrophiliccompound is set as the first end, and the other end is set as the secondend, the hydrophilic compound has the functional group that reacts withthe reactive functional group of the silane coupling agent at the firstend of the molecular chain, and has the sulfonic acid group or thealkali metal salt of the sulfonic acid group at the second end of themolecular chain. The hydrophilic compound does not have a hydrophilicportion other than the functional group that reacts with the reactivefunctional group of the silane coupling agent, and the sulfonic acidgroup.

[10] The hydrophilic treatment coating composition according to [8] or[9] may further contain a reaction catalyst that promotes a reactionbetween the reactive functional group of the silane coupling agent andthe functional group of the hydrophilic compound.

[11] In the hydrophilic treatment coating composition according to anyone of [8] to [10], a number-average molecular weight of the hydrophiliccompound may be 70 to 500.

[12] In the hydrophilic treatment coating composition according to anyone of [8] to [11], the compatibilizer may be at least one kind selectedfrom an amide compound, an aprotic polar solvent, polyhydric alcohol,saccharides, a polar resin, and inorganic salts.

According to a fourth aspect of the invention, there are provided thefollowing hydrophilic treatment methods of [13] and [14].

[13] A hydrophilic treatment method including: treating a surface layerthat contains an inorganic compound with a silane coupling agent thatcontains at least one reactive functional group selected from anisocyanate group, an epoxy group, an amino group, and a mercapto group;applying a hydrophilic treatment coating composition to a surface layerthat is coupled with the silane coupling agent, the hydrophilictreatment coating composition containing a hydrophilic compound thatcontains a functional group that is at least one selected from an aminogroup, a hydroxyl group, and a mercapto group, and reacts with thereactive functional group of the silane coupling agent, and sulfonicacid or an alkali metal salt of the sulfonic acid group, and which doesnot contain a hydrophilic portion at a site other than an end of amolecular chain, and a polar compatibilizer; and allowing the reactivefunctional group of the silane coupling agent and the functional groupof the hydrophilic compound to react with each other by heat.

Here, the meaning of the “hydrophilic portion” is the same as indescription of [8].

The hydrophilic compound is the same as the hydrophilic compounddescribed in [8], and is preferably an appropriate hydrophilic compounddescribed in [8].

[14] A hydrophilic treatment method including: treating a surface layerthat contains an inorganic compound with a silane coupling agent thatcontains at least one reactive functional group selected from anisocyanate group, an epoxy group, an amino group, and a mercapto group;applying a hydrophilic treatment coating composition to the surfacelayer that is coupled with the silane coupling agent, the hydrophilictreatment coating composition containing a hydrophilic compound thatcontains a functional group that is at least one selected from an aminogroup, a hydroxyl group, and a mercapto group, and reacts with thereactive functional group of the silane coupling agent, and a sulfonicacid group, and which does not contain a hydrophilic portion at a siteother than an end of a molecular chain, and a polar compatibilizer;allowing the reactive functional group of the silane coupling agent andthe functional group of the hydrophilic compound to react with eachother with heat; and allowing the sulfonic acid group of the hydrophiliccompound to react with a hydroxide of an alkali metal to formsulphonate.

Here, the meaning of the “hydrophilic portion” is the same as in thedescription of [8].

When one end of a molecular chain of the hydrophilic compound is set asa first end, and the other end is set as a second end, the hydrophiliccompound has the functional group that is at least one selected theamino group, the hydroxyl group, and the mercapto group, and reacts withthe reactive functional group of the silane coupling agent at the firstend of the molecular chain, and has the sulfonic acid group at thesecond end of the molecular chain. The hydrophilic compound does nothave a hydrophilic portion at a site other than the first end and thesecond end.

That is, when the one end of the molecular chain of the hydrophiliccompound is set as the first end, and the other end is set as the secondend, the hydrophilic compound has the functional group that reacts withthe reactive functional group of the silane coupling agent at the firstend of the molecular chain, and has the sulfonic acid group at thesecond end of the molecular chain. The hydrophilic compound does nothave a hydrophilic portion other than the functional group that reactswith the reactive functional group of the silane coupling agent, and thesulfonic acid group.

Advantageous Effects of Invention

According to the aspects of the invention, it is possible to reduce thenumber of washing times by preventing an inorganic material such ascalcium from being settled to crockery such as toilet bowl and awashstand which are installed in a water-using site in a building andcontains an inorganic compound such as silicon oxide, and by makingwashing of an oily contaminant, which becomes a cause for propagation ofa fungi and an offensive odor, easy.

DESCRIPTION OF EMBODIMENTS

<First Aspect and Second Aspect>

Hereinafter, detailed description will be given of an embodiment of ahydrophilic treatment coating composition and a hydrophilic treatmentmethod according to a first aspect and a second aspect of the invention.Furthermore, expressions indicating a range of a quantity include anupper limit and a lower limit.

Typically, with regard to crockery such as a toilet bowl and a washstandwhich are installed at a water-using site in a building, the followingsurface treatment is performed. Specifically, glaze such as ash glaze isapplied to a surface of unglazed crockery, and firing is performed toform a vitreous layer on the surface of the crockery. When the surfacetreatment with the glaze is performed, a plurality of silicon oxides,which are inorganic compounds, exist on the surface layer, and thus aplurality of silanol groups also exist.

In a previous step of application of the hydrophilic treatment coatingcomposition of the first aspect of the invention, a primer layer, whichis obtained by treating the surface layer of crockery with a silanecoupling agent that contains a radical reactive functional group, may beprovided. The primer layer is located between the surface layer of thecrockery and the hydrophilic treatment coating composition of the firstaspect of the invention, and functions as a binder that couples a partof the hydrophilic treatment coating composition of the first aspect ofthe invention to the surface layer of the crockery.

Preferred examples of the radical reactive functional group in thesilane coupling agent that contains the radical reactive functionalgroup include an acryloyl group, a methacryloyl group, a vinyl group, anallyl group, a styryl group, and a mercapto group. As specific examplesof the silane coupling agent, 3-acryloxypropyltrimethoxysilane,vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane,3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-methacryloxypropyltriethoxysilane,3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane,and the like. In addition, as a hydrolyzable group that is coupled to asilicon atom, in addition to the alkoxy group such as the methoxy groupand the ethoxy group, a 2-methoxyethoxyl group (CH₃OCH₂CH₂—O—) may beprovided. As a commercially available product thereof, KBM-5103,KBM-1003, KBE-1003, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503,KBM-802, and KBM-803 which are manufactured by Shin-Etsu Chemical Co.,Ltd., and the like can be used.

The alkoxy silane of the silane coupling agent that contains the radicalreactive functional group is hydrolyzed, and a silanol group that isgenerated is subjected to a dehydration and condensation reaction with asilanol group that exists on the surface layer of crockery. At thistime, preferred examples of a catalyst that hydrolyzes the alkoxy silaneinclude an acidic catalyst such as an aqueous hydrochloric acidsolution, an aqueous sulfuric acid solution, an aqueous nitric acidsolution, an aqueous phosphoric acid solution, and an aqueous solutionof a compound having a carboxylic acid such as formic acid, acetic acidand propionic acid, a basic catalyst such as an aqueous ammoniasolution, morpholine, N-methylmorpholine, N-ethylmorpholine, piperazine,hydroxyethylpiperazine, 2-methylpiperazine, trans2,5-dimethylpiperazine, cis 2,6-dimethylpiperazine, triethylamine,N,N-dimethylethanolamine, N,N-diethylethanolamine,N-(β-aminoethyl)ethanolamine, N-methyldiethanolamine,N-n-butylethanolamine, N-n-butyldiethanolamine, N-t-butylethanolamine,N-t-butyldiethanolamine, N-(β-aminoethyl)isopropanolamine,N,N-diethylisopropanolamine, 2-amino-2-methyl-1-propanol, an aqueoussodium hydroxide solution, and an aqueous potassium hydroxide solution.

In addition, as a solvent of a composition that is used to form theprimer layer, for example, the following organic solvents and water arepreferable. Examples of the organic solvents include alcohols such asmethanol, ethanol, isopropyl alcohol, n-propyl alcohol, and1-methoxy-2-propanol, ketones such as methylethylketone andmethylisobutylketone, and esters such as ethyl acetate.

In the composition that is used to form the primer layer, it ispreferable that a blending amount of the silane coupling agent thatcontains the radical reactive functional group with respect to a totalweight of the composition is 0.01 to 10% by weight, more preferably 0.05to 5% by weight, and still more preferably 0.1 to 2% by weight. When theblending amount of the silane coupling agent that contains the radicalreactive functional group is less than 0.01% by weight, the primer layeris not sufficiently formed, and a hydrophilic compound that issubsequently coupled to the silane coupling agent decreases, and thushydrophilicity decreases. In addition, when the blending amount of thesilane coupling agent that contains the radical reactive functionalgroup is greater than 10% by weight, the coupling agent is subjected toa condensation reaction, and thus gelation occurs, or unevenness occursin the primer layer.

Specifically, the primer layer is formed as follows as an example.

Primer Layer 1A

0.5 parts by weight of 3-acryloxypropyltrimethoxysilane, and 99 parts byweight of 1-methoxy-2-propanol are stirred and mixed at roomtemperature, and 0.5 parts by weight of 3% hydrochloric acid aqueoussolution is added to the resultant mixture. Then, the resultant mixtureis stirred for 30 minutes for hydrolysis. A solution that is obtained isapplied to the surface layer of crockery, and the crockery is leftstationary at 60° C. for 30 minutes by using an electric oven tovolatilize a solvent and the like by using heat, and to subject asilanol group generated from the 3-acryloxypropyltrimethoxysilane and asilanol group of the surface layer of the crockery to a dehydration andcondensation reaction, thereby obtaining the primer layer.

Primer Layer 2A

0.5 parts by weight of vinyltrimethoxysilane, and 99 parts by weight of1-methoxy-2-propanol are stirred and mixed at room temperature, and then0.5 parts by weight of 3% hydrochloric acid aqueous solution is added tothe resultant mixture. Then, the resultant mixture is stirred for 30minutes for hydrolysis. A solution that is obtained is applied to thesurface layer of the crockery, and the crockery is left stationary at60° C. for 30 minutes by using an electric oven to volatilize a solventand the like by using heat, and to subject a silanol group generatedfrom the vinylmethoxysilane and a silanol group of the surface layer ofthe crockery to a dehydration and condensation reaction, therebyobtaining the primer layer.

Primer Layer 3A

0.5 parts by weight of p-styryltrimethoxysilane, and 99 parts by weightof 1-methoxy-2-propanol are stirred and mixed at room temperature, andthen 0.5 parts by weight of 3% hydrochloric acid aqueous solution isadded to the resultant mixture. Then, the resultant mixture is stirredfor 30 minutes for hydrolysis. A solution that is obtained is applied tothe surface layer of the crockery, and the crockery is left stationaryat 60° C. for 30 minutes by using an electric oven to volatilize asolvent and the like by using heat, and to subject a silanol groupgenerated from the p-styryltrimethoxysilane and a silanol group of thesurface layer of the crockery to a dehydration and condensationreaction, thereby obtaining the primer layer.

Primer Layer 4A

0.5 parts by weight of 3-methacryloxypropyltrimethoxysilane, and 99parts by weight of 1-methoxy-2-propanol are stirred and mixed at roomtemperature, and then 0.5 parts by weight of 3% hydrochloric acidaqueous solution is added to the resultant mixture. Then, the resultantmixture is stirred for 30 minutes for hydrolysis. A solution that isobtained is applied to the surface layer of the crockery, and thecrockery is left stationary at 60° C. for 30 minutes by using anelectric oven to volatilize a solvent and the like by using heat, and tosubject a silanol group generated from the3-methacryloxypropyltrimethoxysilane and a silanol group of the surfacelayer of the crockery to a dehydration and condensation reaction,thereby obtaining the primer layer.

Primer Layer 5A

0.5 parts by weight of 3-mercaptopropyltrimethoxysilane, and 99 parts byweight of 1-methoxy-2-propanol are stirred and mixed at roomtemperature, and then 0.5 parts by weight of 3% hydrochloric acidaqueous solution is added to the resultant mixture. Then, the resultantmixture is stirred for 30 minutes for hydrolysis. A solution that isobtained is applied to the surface layer of the crockery, and thecrockery is left stationary at 60° C. for 30 minutes by using anelectric oven to volatilize a solvent and the like by using heat, and tosubject a silanol group generated from the3-mercaptopropyltrimethoxysilane and a silanol group of the surfacelayer of the crockery to a dehydration and condensation reaction,thereby obtaining the primer layer.

With respect to each of the primer layers obtained as described above,the following surface treatment is performed. In the surface treatment,the hydrophilic treatment coating composition of the first aspect of theinvention is subjected to a reaction with the primer layer by usingultraviolet rays or heat. The hydrophilic treatment coating compositioncontains a hydrophilic compound (A) that contains a radical reactivefunctional group, and an alkali metal salt of a sulfonic acid group,does not contain a hydrophilic portion at a site other than an end of amolecular chain, and does not contains a branched chain, a radicalpolymerization initiator, and a polar compatibilizer.

Here, “does not contain a branched chain” represents that thehydrophilic compound (A) does not have a branched chain having 5 or morecarbon atoms, and preferably does not have a branched chain having 3 ormore carbon atoms. However, the hydrophilic compound (A) may have abranched chain having 2 or less carbon atoms. That is, in the invention,a side chain having 2 or less carbon atoms is not included in (is notclassified to) the branched chain. If the hydrophilic compound (A) has abranched chain having 5 or more carbon atoms, a hydrophilic portion isless likely to concentrate on the surface, and thus sufficientwashability is not exhibited.

The hydrophilic compound (A) has a radical reactive functional groupthat reacts with the radical reactive functional group of the silanecoupling agent at one end, and the alkali metal salt of the sulfonicacid group at the other end, does not have a hydrophilic group at a siteother than the end of the molecular chain, and does not have a branchedchain. In this structure, the hydrophilic group of the hydrophiliccompound (A) is allowed to concentrate on a surface of a coated film,and thus even when being used in crockery such as a toilet bowl and awashstand which are frequently washed with water, it is possible toprovide sufficient washability.

Preferred examples of the radical reactive functional group at the oneend of the hydrophilic compound (A) include an acryloyl group, amethacryloyl group, a vinyl group, an allyl group, a styryl group, amercapto group, and the like. Preferred examples of the alkali metalsalt of the sulfonic acid group at the other end include a sodium saltand a potassium salt. Preferred specific examples of the hydrophiliccompound (A) include sodium N-t-butyl acrylamide sulfonate, sodium vinylsulfonate, 2-sodium sulfoethyl methacrylate, sodium allyl sulfonate,sodium p-styrene sulfonate, sodium 3-mercapto-1-propane sulfonate, andthe like. With regard to properties of the hydrophilic compound (A), asolid substance, an aqueous solution, and the like can be used. As acommercially available product of the hydrophilic compound (A), ATBS(registered trademark)-Na manufactured by Toagosei Co., Ltd., N-SVS-25manufactured by Asahi Kasei Finechem Co., Ltd., Antox MS-2N manufacturedby Nippon Nyukazai Co., LTd., Spinomar (registered trademark) NaSSmanufactured by Tosoh Organic Chemical Co., Ltd., and the like can beused. In addition, in addition to the commercially available product,the hydrophilic compound (A) can be synthesized. For example, ahydrophilic compound, which is obtained by synthesizing sodiumsulfonate-containing urethane acrylate, potassium N-t-butyl acrylamidesulfonate, and the like, can be used.

For example, the sodium sulfonate-containing urethane acrylate can besynthesized as follows.

Synthesis Example 1

45.2 parts by weight of aminoethyl sulfonate, 14.8 parts by weight ofsodium hydroxide, and 40 parts by ion exchanged water are allowed toreact with each other at room temperature of 20 to 25° C. 42.5 parts byweight of the resultant solution is maintained at a temperature of 5 to10° C., and a solution, which is obtained by mixing and dissolving 24.5parts by weight of 2-isocyanatoethyl acrylate (Karenz AOI (registeredtrademark)) manufactured by Showa Denko K. K. in 33 parts by weight of1-methoxy-2-propanol, is added dropwise to the resultant solution for 5minutes. Then, the resultant solution is stirred for 4 hours forsynthesis. From the infrared absorption spectrum, it is confirmed thatreaction is terminated without recognition of absorption derived from anisocyanate group.

In addition, for example, the potassium N-t-butyl acrylamide sulfonatecan be synthesized as follows.

Synthesis Example 2

49.1 parts by weight of ion exchanged water, 40.0 parts by weight ofN-t-butylacrylamide sulfonic acid (ATBS (registered trademark),manufactured by Toagosei Co., Ltd.), and 10.9 parts by weight ofpotassium hydroxide are mixed, and the resultant mixture is stirred atroom temperature of 20 to 25° C. for 1 hour for synthesis. Terminationof a reaction is confirmed when pH reaches a neutral region.

It is preferable that a number-average molecular weight of thehydrophilic compound (A) is 70 to 500, and more preferably 130 to 400.When the number-average molecular weight of the hydrophilic compound (A)is less than 70, it is difficult for an existing raw material to containa radical reactive functional group and an alkali metal salt of asulfonic acid group, and thus it is difficult to form a hydrophiliccoated film. When the number-average molecular weight of the hydrophiliccompound (A) is greater than 500, the amount of a sulfonic acid metalsalt in the coated film decreases, and thus the hydrophilicity becomesdeficient.

In addition, the following treatment may be performed with respect tothe radical reactive functional group of the primer layer. Specifically,the radical reactive functional group is allowed to react with acompound such as N-t-butylacrylamide sulfonic acid that has a radicalreactive functional group at one end and sulfonic acid at the other end,does not have a hydrophilic portion at a site other than an end of amolecular chain, and does not have a branched chain so as to form acarbon-carbon bond. Then, neutralization is performed with an aqueoushydroxide solution of an alkali metal such as sodium hydroxide andpotassium hydroxide so as to form a sulfonate.

A solvent may be added to the hydrophilic treatment coating compositionof the first aspect of the invention so as to dissolve or disperse thehydrophilic compound (A). Preferred examples of the solvent includewater, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and thelike. It is preferable to adjust a solid content concentration of thehydrophilic compound (A) with respect to a total weight of thecomposition to 0.1 to 60% by weight through addition of the solvent.When the solid content concentration of the hydrophilic compound (A) isless than 0.1% by weight, a hydrophilic group in a coated film that isformed decreases, and thus hydrophilicity decreases. In addition, whenthe solid content concentration of the hydrophilic compound (A) isgreater than 60% by weight, it is difficult to uniformly mix the solventthat dissolves or disperses the hydrophilic compound (A), the radicalpolymerization initiator, and the polar compatibilizer, and thusconstant hydrophilicity is not provided.

The radical polymerization initiator is a compound that is decomposedwith light or heat to generate a radical. The radical polymerizationinitiator is classified into an optical radical polymerization initiatorthat is decomposed with light, and a thermal radical polymerizationinitiator that is decomposed with heat. It is preferable that theradical polymerization initiator is soluble in water.

Preferred examples of the optical radical polymerization initiatorinclude benzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, a mixture of1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one,2-hydroxy-2-methyl-1-phenyl-propane-1-one,2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)-benzyl}phenyl]-2-methyl-1-propane-1-one,oxy-phenyl acetate, a mixture of 2-[2-oxo-2-phenylacetoxyethoxy]ethylester, oxy-phenyl acetate, and 2-(2-hydroxyethoxy)ethyl ester,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like. Inaddition, a sensitizer such as p-dimethyl amino benzoic acid ethyl(KAYACURE EPA, manufactured by Nippon Kayaku Co., Ltd.) may be added tothe optical radical polymerization initiator as necessary. As acommercially available product of the optical radical polymerizationinitiator, for example, IRGACURE (registered trademark) 184, IRGACURE(registered trademark) 500, IRGACURE (registered trademark) 2959,DAROCURE (registered trademark) 1173, IRGACURE (registered trademark)127, IRGACURE (registered trademark) 754, and IRGACURE (registeredtrademark) 819DW which are manufactured by BASF, and the like can beused.

As the thermal radical polymerization initiator, for example, anazo-based compound such as2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride,2,2′-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate,2,2′-azobis[2-(2-imidazolin-2-yl)propane],2,2′-azobis(propan-2-carboamidine)dihydrochloride, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n-hydrate,2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and4,4′-azobis(4-cyanopentanoic acid), sodium persulfate such as ammoniumpersulfate, sodium persulfate, and potassium persulfate, peroxide suchas hydrogen peroxide, cumyl perneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t-hexylperoxy neodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxy pivalate, and t-butyl peroxy pivalate, andthe like are preferable. In addition, water and the like may be added tothe thermal radical polymerization initiator as necessary. As acommercially available product thereof, for example, VA-044, VA-046B,VA-061, V-50, VA-057, VA-086, and V-501 which are manufactured by WakoPure Chemical Industries, Ltd., Percumyl ND-50E, Perocta ND-50E,Perhexyl ND-50E, Perbutyl ND-50E, perhexyl PV-50E, Perbutyl PV-40E whichare manufactured by NOF CORPORATION, and reagents of respectivecompanies and the like can be used.

It is preferable that a blending amount of the radical polymerizationinitiator is 0.1 to 50% by weight with respect to the solid contentweight (100% by weight) of the hydrophilic compound (A), and morepreferably 1 to 20% by weight. When the blending amount of the radicalpolymerization initiator is less than 0.1% by weight, radicals aregenerated in a small amount, and thus it is difficult for the radicalreactive functional group of the hydrophilic compound (A) tosufficiently react with the radical. As a result, hydrophilic groups arepresent in the coated film that is formed in a small amount, and thushydrophilicity decreases. In addition, when the blending amount of theradical polymerization initiator is greater than 50% by weight, theradicals are excessively generated, and thus the molecular weightdecreases. As a result, hydrophilicity of the coated film that is formeddecreases.

Typically, when manufacturing a composition by using the hydrophiliccompound (A) that does not contain a hydrophilic portion at a site otherthan an end of a molecular chain, and does not contain a branched chainwithout using the compatibilizer, components of the composition arecrystallized, and thus a coated film is not uniform. Therefore,hydrophilicity of a coated film that is formed may not be sufficient, orunevenness may occur. On the other hand, when the compatibilizer isblended to the composition, crystallization of the hydrophilic compound(A), which does not contain a hydrophilic portion at a site other thanan end of a molecular chain, and does not contain a branched chain, issuppressed, and thus it is possible to obtain a uniform coated film.

Preferred examples of the compatibilizer include an amide compound suchas urea, melamine, acryloyl morpholine, dimethyl acrylamide,dimethylaminopropyl acrylamide, isopropyl acrylamide, diethylacrylamide, and hydroxyethyl acrylamide, aprotic polar solvents such asdimethyl sulfoxide, acetonitrile, and N,N-dimethylformamide, polyhydricalcohol such as ethylene glycol, glycerin, trimethylolpropane,ditrimethylolpropane, erythritol, erythritol, and dipentaerythritol,saccharides such as triose, tetrose, pentose, hexose, sedoheptulose,glucose, maltose, sucrose, lactose, cellobiose, raffinose, acarbose,oligosaccharides, cyclodextrin, dextrin, and starch, a polar resin suchas sodium carboxymethyl cellulose, polyvinyl pyrrolidone, sodiumpolyacrylate, and modified urea, and inorganic salts such as sodiumhydrogen carbonate, sodium carbonate, sodium hydrogen sulfate, andsodium sulfate. As a commercially available product thereof, reagents ofrespective companies can be used. With regard to the resin, for example,Cellogen WS-C, Pitts call K-30L, Shallol DC-902P, and Shallol DC-303PShallol which are manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.,BYKETOL-PC manufactured by BYK Japan KK., and the like can be used. Inaddition, one or more kinds of the compatibilizers may be mixed andused.

For example, an aqueous solution of the sodium carboxymethyl cellulosemay be adjusted as follows.

Adjustment Example 1

30.0 parts by weight of sodium carboxylmethyl cellulose (100 wt % solidcontent, Cellogen WS-C manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)is stirred and dissolved in 70 parts by weight of ion exchanged water ata liquid temperature of 20 to 25° C. for 24 hours.

It is preferable that a blending amount of the compatibilizer is 10 to200% by weight with respect to the solid content weight (100% by weight)of the hydrophilic compound, and more preferably 30 to 120% by weight.When the blending amount of the compatibilizer is less than 10% byweight, the hydrophilic compound is crystallized and powderized, andthus a reaction rate decreases. As a result, hydrophilicity of a coatedfilm that is formed decreases. When the blending amount of thecompatibilizer is greater than 200% by weight, a concentration of thehydrophilic compound is relatively lowered, and thus a reaction ratedecreases. As a result, hydrophilicity of a coated film that is formeddecreases.

The hydrophilic treatment coating composition of the first aspect of theinvention may further contain other additives in addition to theabove-described components. As the other additives, a surfaceconditioner, a leveling agent, a plasticizer, an antifoaming agent, anultraviolet absorbing agent, an antioxidant, a viscosity modifier, andthe like can be used. In addition, the additives can be used incombination of two or more kinds.

In the second aspect of the invention, ultraviolet rays or heat is usedso as to allow the hydrophilic treatment coating composition of thefirst aspect of the invention and the primer layer to react with eachother. As an ultraviolet ray irradiation apparatus, for example, ahigh-pressure mercury lamp, a metal halide lamp, an ultraviolet LED(UV-LED) lamp having a light-emitting wavelength in which a peakwavelength is 405 nm or less, and the like may be used alone or incombination of a plurality of kinds thereof. The amount of ultravioletrays required for radical polymerization with ultraviolet rays ismeasured by using an integral actinometer. In addition, as an apparatusthat generates heat, an electric oven, a hot air drier, an infrared rayirradiation apparatus, and the like can be used.

Components, which remain on the coated film formed through reactionbetween the hydrophilic treatment coating composition of the firstaspect of the invention and the primer layer without reacting with theprimer layer, are washed with water and the like, and the hydrophilictreatment of the second aspect of the invention is terminated.

In the second aspect of the invention, the primer layer may not beprovided in advance. As a composition that is allowed to react with asurface layer, which contains an inorganic compound, of crockery and thelike, a hydrophilic treatment coating composition, which contains thesilane coupling agent, the hydrophilic compound, and the compatibilizer,may be used. According to a method of using this composition, it ispossible to perform a primer treatment process with the silane couplingagent, and a hydrophilic treatment process of allowing the hydrophiliccompound to react with the silane coupling agent at once. Accordingly,for example, when using the composition with respect to crockery such asa toilet bowl and a washstand which are installed already in house oroffice, it is possible to shorten working time at an installation siteof the crockery.

In the second aspect of the invention, a first liquid that contains thesilane coupling agent and the like, and a second liquid that containsthe hydrophilic compound (A), the compatibilizer, and the like may beseparately prepared. Immediately before performing work with respect tothe surface layer, the first liquid and the second liquid may be mixedand used. When the first liquid and the second liquid are separatelyprepared in advance, it is possible to suppress hydrolysis of the silanecoupling agent due to a catalytic operation of the functional group ofthe hydrophilic compound (A) during storage before use. Accordingly, itis possible to suppress a decrease in reactivity with the surface layerdue to dehydration and condensation between silanol groups which aregenerated during storage, and it is possible to prevent particulatesfrom being generated. In addition, the second liquid may contain acatalyst that promotes hydrolysis of the silane coupling agent in alkoxysilane.

<Third Aspect and Fourth Aspect>

Hereinafter, detailed description will be given of an embodimentpertaining to a hydrophilic treatment coating composition and ahydrophilic treatment method according to a third aspect and a fourthaspect of the invention. Furthermore, expressions indicating a range ofa quantity include an upper limit and a lower limit.

In a previous step of application of the hydrophilic treatment coatingcomposition of the third aspect of the invention, a primer layer, whichis obtained by treating the surface layer of crockery with a silanecoupling agent that contains at least one reactive functional groupselected from an isocyanate group, an epoxy group, an amino group, and amercapto group, may be provided. The primer layer is located between thesurface layer of the crockery and the hydrophilic treatment coatingcomposition of the third aspect of the invention, and functions as abinder that couples a part of the hydrophilic treatment coatingcomposition of the third aspect of the invention to the surface layer ofthe crockery.

Preferred specific examples of the silane coupling agent that containsat least one reactive functional group selected from the isocyanategroup, the epoxy group, the amino group, and the mercapto group include3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,3-glycidoxypropylmethyldimethoxysilane,3-glycidoxypropyltrimethoxysilane,3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane,N-2-(aminoethyl)-3-aminopropylmethyldimetoxysilane,N-2-(aminoethyl)-3-aminopropyltriethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine,N-phenyl-3-aminopropyltrimethoxysilane, a hydrochloride ofN-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane,3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane,and the like. In addition, as a hydrolyzable group that is coupled to asilicon atom, in addition to the alkoxy group such as the methoxy groupand the ethoxy group, a 2-methoxyethoxyl group (CH₃OCH₂CH₂—O—) may beprovided. As a commercially available product of the silane couplingagent, KBE-9007, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-602,KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-802, andKBM-803 which are manufactured by Shin-Etsu Chemical Co., Ltd., Y-5187manufactured by Momentive Performance Materials Inc., and the like canbe used.

The alkoxy silane of the silane coupling agent is hydrolyzed, and asilanol group that is generated is subjected to a dehydration andcondensation reaction with a silanol group that exists on the surfacelayer of the crockery. At this time, as a catalyst that hydrolyzes thealkoxy silane, for example, catalysts which are exemplified in the firstaspect are preferable.

In addition, as a solvent of a composition that is used to form theprimer layer, the solvents which are exemplified in the first aspect arepreferable.

In the composition that is used to form the primer layer, it ispreferable that a blending amount of the silane coupling agent withrespect to a total weight of the composition is 0.01 to 10% by weight,more preferably 0.05 to 5% by weight, and still more preferably 0.1 to2% by weight. When the blending amount of the silane coupling agent isless than 0.01% by weight, the primer layer is not sufficiently formed,and a hydrophilic compound that is subsequently coupled to the silanecoupling agent decreases, and thus hydrophilicity decreases. Inaddition, when the blending amount of the silane coupling agent isgreater than 10% by weight, the coupling agent is subjected to acondensation reaction, and thus gelation occurs, or unevenness occurs inthe primer layer.

Specifically, the primer layer is formed as follows as an example.

Primer Layer 1B

0.5 parts by weight of 3-i socyanatopropyltrimethoxysilane, and 99 partsby weight of 1-methoxy-2-propanol are stirred and mixed at roomtemperature, and then 0.5 parts by weight of 3% hydrochloric acidaqueous solution is added to the resultant mixture. Then, the resultantmixture is stirred for 30 minutes for hydrolysis. A solution that isobtained is applied to a surface layer of crockery that is degreasedwith methanol in advance, and the crockery is left stationary at 60° C.for 30 minutes by using an electric oven to volatilize a solvent and thelike by using heat, and to subject a silanol group generated from the3-isocyanatopropyltrimethoxysilane and a silanol group of the surfacelayer of the crockery to a dehydration and condensation reaction,thereby obtaining the primer layer.

Primer Layer 2B

0.5 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 99 partsby weight of 1-methoxy-2-propanol are stirred and mixed at roomtemperature, and then 0.5 parts by weight of 3% hydrochloric acidaqueous solution is added to the resultant mixture. Then, the resultantmixture is stirred for 30 minutes for hydrolysis. A solution that isobtained is applied to a surface layer of crockery, and the crockery isleft stationary at 60° C. for 30 minutes by using an electric oven tovolatilize a solvent and the like by using heat, and to subject asilanol group generated from the vinylmethoxysilane and a silanol groupof the surface layer of the crockery to a dehydration and condensationreaction, thereby obtaining the primer layer.

With respect to the primer layer obtained as described above, thefollowing surface treatment is performed. In the surface treatment, thehydrophilic treatment coating composition of the third aspect of theinvention is subjected to a reaction with the primer layer. Thehydrophilic treatment coating composition contains: a hydrophiliccompound (B) which contains a functional group that is at least oneselected from an amino group, a hydroxyl group, a mercapto group, and anepoxy group, and reacts with the reactive functional group of the silanecoupling agent, and an alkali metal salt of a sulfonic acid group, andwhich does not contain a hydrophilic portion at a site other than an endof a molecular chain; and a polar compatibilizer.

The hydrophilic compound (B) has at least one functional group, which isselected from an amino group, a hydroxyl group, a mercapto group, and anepoxy group, and reacts with at least one reactive functional groupselected from an isocyanate group, an epoxy group, an amino group, and amercapto group of the silane coupling agent, at one end, and sulfonicacid or an alkali metal salt of a sulfonic acid group at the other end,and does not have a hydrophilic group at a site other than an end of amolecular chain. In this structure, the hydrophilic group of thehydrophilic compound (B) is allowed to concentrate on a surface of acoated film, and thus even when being used in crockery such as a toiletbowl and a washstand which are frequently washed with water, it ispossible to provide sufficient washability. In addition, it is morepreferable that the hydrophilic compound (B) does not have a branchedchain so as to allow the hydrophilic group to orient in a specificdirection.

Here, it is preferable that the hydrophilic compound (B) does not have abranched chain having 5 or more carbon atoms. More preferably, thehydrophilic compound (B) does not have a branched chain having 3 or morecarbon atoms. However, the hydrophilic compound (B) may have a branchedchain having 2 or less carbon atoms. That is, in the invention, a sidechain having 2 or less carbon atoms is not included in (is notclassified to) the branched chain. If the hydrophilic compound (B) has abranched chain having 5 or more carbon atoms, a hydrophilic portion isless likely to concentrate on the surface, and thus sufficientwashability may not be exhibited.

As the alkali metal salt of the sulfonic acid group which exists at theother end of the hydrophilic compound (B), for example, a sodium saltand a potassium salt are preferable. Preferred specific examples of thehydrophilic compound (B) include sodium 2-aminoethyl sulfonate,potassium 2-aminoethyl sulfonate, sodium 4-aminobenzene sulfonate,sodium 2-hydroxyethyl sulfonate, sodium 3-mercapto-1-propane sulfonate,sodium 2-glycidylethyl sulfonate, sodium aminosulfonate, potassiumaminosulfonate, amine methane sulfonic acid, 3-aminopropane sulfonicacid, 2-aminobenzenesulfonic acid, 4-aminobenzene sulfonic acid, sodiumhydroxy methane sulfonate, 4-hydroxy-1-butane sulfonic acid, and thelike. With regard to properties of the hydrophilic compound (B), a solidsubstance, an aqueous solution, and the like can be used. Theabove-described various sulfonic acids may be subjected to aneutralization reaction with sodium hydroxide, potassium hydroxide, andthe like for synthesis, and the resultant product may be used.

For example, the sodium 2-aminoethyl sulfonate can be synthesized asfollows.

Synthesis Example 3

37.9 parts by weight of 2-aminoethyl sulfonate, 12.1 parts by weight ofsodium hydroxide, 50.2 parts by weight of ion exchanged water arestirred at room temperature of 20 to 25° C. for 1 hours for synthesis.Termination of a reaction is confirmed when pH reaches a neutral region.

In addition, with regard to potassium 2-aminoethyl sulfonate, sodium4-aminobenzene sulfonate, sodium 2-hydroxyethyl sulfonate, sodium3-mercapto-1-propane sulfonate, sodium 2-glycidylethyl sulfonate, andthe like, synthesis can be performed in the same manner as in SynthesisExample 3.

It is preferable that number-average molecular weight of the hydrophiliccompound (B) is 70 to 500, and more preferably 100 to 400. When thenumber-average molecular weight of the hydrophilic compound (B) is lessthan 70, it is difficult for the hydrophilic compound (B) to contain atleast one functional group selected from an amino group, a hydroxylgroup, a mercapto group, and an epoxy group, and an alkali metal salt ofthe sulfonic acid group, and it is difficult to form a hydrophiliccoated film. When the number-average molecular weight of the hydrophiliccompound (B) is greater than 500, a reaction rate decreases due tosteric hindrance, and the amount of hydrophilic groups decreases. As aresult, hydrophilicity of the coated film decreases.

In addition, the following treatment may be performed with respect to atleast one reactive functional group selected from an isocyanate group,an epoxy group, an amino group, and a mercapto group of the primerlayer. Specifically, the reactive functional group is allowed to reactwith a compound such as 2-aminoethyl sulfonic acid that has at least onefunctional group selected from an amino group, a hydroxyl group, amercapto group, and epoxy group at one end, has sulfonic acid at theother end, and does not have a hydrophilic portion at a portion otherthan an end of a molecular chain. Then, neutralization is performed withan aqueous hydroxide solution of an alkali metal such as sodiumhydroxide and potassium hydroxide so as to form a sulfonate.

A solvent may be added to the hydrophilic treatment coating compositionof the third aspect of the invention so as to dissolve or disperse thehydrophilic compound (B). Preferred examples of the solvent includewater, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and thelike. It is preferable to adjust a solid content concentration of thehydrophilic compound (B) with respect to a total weight of thecomposition to 0.1 to 60% by weight through addition of the solvent.When the solid content concentration of the hydrophilic compound (B) isless than 0.1% by weight, the number of hydrophilic groups in a coatedfilm that is formed decreases, and thus hydrophilicity decreases. Inaddition, when the solid content concentration of the hydrophiliccompound (B) is greater than 60% by weight, it is difficult to uniformlymix the solvent that dissolves or disperses the hydrophilic compound(B), and the polar compatibilizer, and thus constant hydrophilicity isnot provided.

The polar compatibilizer is a material that can uniformly dissolve thehydrophilic compound (B) without crystallization of the hydrophiliccompound (B). Typically, when manufacturing a composition by using thehydrophilic compound (B) that does not contain a hydrophilic portion ata site other than an end of a molecular chain without using thecompatibilizer, components of the composition are crystallized, and thusa composition is not uniform. Therefore, hydrophilicity of a coated filmthat is formed may not be sufficient, or unevenness may occur. On theother hand, when the compatibilizer is blended to the composition,crystallization of the hydrophilic compound (B), which does not containa hydrophilic portion at a site other than an end of a molecular chain,is suppressed, and thus it is possible to obtain a composition that isuniformly dissolved.

As the compatibilizer, for example, the compatibilizers exemplified inthe first aspect are preferable.

It is preferable that the blending amount of the compatibilizer is 10 to200% by weight with respect to a solid-content weight (100% by weight)of the hydrophilic compound, and more preferably 30 to 120% by weight.When the blending amount of the compatibilizer is less than 10% byweight, the hydrophilic compound is crystallized and powderized, andthus a reaction rate decreases. As a result, hydrophilicity of a coatedfilm that is formed decreases. When the blending amount of thecompatibilizer is greater than 200% by weight, a concentration of thehydrophilic compound is relatively lowered, and thus a reaction ratedecreases. As a result, hydrophilicity of a coated film that is formeddecreases.

In addition, a reaction catalyst may be blended to the hydrophilictreatment coating composition of the third aspect of the invention so asto promote a reaction between the silane coupling agent and thehydrophilic compound (B). For example, when allowing a silane couplingagent having an isocyanate group and a hydrophilic compound having ahydroxyl group to react with each other, it is preferable to use anorganic tin catalyst such as tin dibutyl dilaurate. In addition, whenallowing a silane coupling agent having a glycidyl group and ahydrophilic compound having a hydroxyl group or a mercapto group toreact with each other, it is preferable to use a compound such asN,N-dimethylbenzylamine, triphenylphosphine, and1,8-diazabicyclo(5,4,0)undesen-7, 2-heptadecylimidazole.

The hydrophilic treatment coating composition of the third aspect of theinvention may contain other additives in addition to the above-describedcomponents. As the other additives, a surface conditioner, a levelingagent, a plasticizer, an antifoaming agent, an ultraviolet absorbingagent, an antioxidant, a viscosity modifier, and the like can be used.In addition, the additives can be used in combination of two or morekinds.

In the fourth aspect of the invention, heat is used so as to allow thehydrophilic treatment coating composition of the third aspect of theinvention and the primer layer to react with each other. As an apparatusthat generates heat, for example, an electric oven, a hot air drier, aninfrared ray irradiation apparatus, and the like can be used. As acommercially available product thereof, UWL-300N manufactured by TRPTRADING CO.,LTD., and the like can be used.

Components, which remain on the coated film formed through reactionbetween the hydrophilic treatment coating composition of the thirdaspect of the invention and the primer layer without reacting with theprimer layer, are washed with water and the like, and the hydrophilictreatment of the fourth aspect of the invention is terminated.

In the fourth aspect of the invention, the primer layer may not beprovided in advance. As a composition that is allowed to react with asurface layer, which contains an inorganic compound, of crockery and thelike, a hydrophilic treatment coating composition, which contains thesilane coupling agent, the hydrophilic compound, and the compatibilizer,may be used. According to a method of using this composition, it ispossible to perform a primer treatment process with the silane couplingagent, and a hydrophilic treatment process of allowing the hydrophiliccompound to react with the silane coupling agent at once. Accordingly,for example, when using the composition with respect to crockery such asa toilet bowl and a washstand which are installed already in house oroffice, it is possible to shorten the working time at an installationsite of the crockery.

In the fourth aspect of the invention, a first liquid that contains thesilane coupling agent and the like, and a second liquid that containsthe hydrophilic compound (B), the compatibilizer, and the like may beseparately prepared. Immediately before performing work with respect tothe surface layer, the first liquid and the second liquid may be mixedand used. When the first liquid and the second liquid are separatelyprepared in advance, it is possible to suppress hydrolysis of the silanecoupling agent due to a catalytic operation of the functional group ofthe hydrophilic compound (B) during storage before use. Accordingly, itis possible to suppress a decrease in reactivity with the surface layerdue to dehydration and condensation between silanol groups which aregenerated during storage, and it is possible to prevent particulatesfrom being generated. In addition, the second liquid may contain acatalyst that promotes hydrolysis of the silane coupling agent in alkoxysilane.

EXAMPLES

Hereinafter, the invention will be described in more detail withreference to Examples and Comparative Examples, but the invention is notlimited thereto.

Hereinafter, a description will be given of Examples 1A to 24A, andComparative Examples 1A to 12A according to the first aspect and thesecond aspect of the invention.

Examples 1A, 2A, and 3A

The following compositions were obtained for reaction with the primerlayer 1A. Specifically, 27.5 parts by weight of ion exchanged water and10 parts by weight of urea were mixed and stirred until the urea wasdissolved. Then, 50.0 parts by weight of sodium N-t-butylacrylamidesulfonate (50 wt % aqueous solution, number-average molecular weight:229), 2.5 parts by weight of IRGACURE (registered trademark) 500 (amixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone)manufactured by BASF, and 10.0 parts by weight of isopropyl alcohol wereadded to the resultant mixture, and this mixture was stirred until atransparent uniform solution was obtained, thereby obtainingcompositions of Examples 1A, 2A, and 3A in an amount of 100 parts byweight.

Example 4A

A composition of Example 4A was obtained in an amount of 100 parts byweight in the same manner as in Example 1A except that 2.5 parts byweight of IRGACURE (registered trademark) 2959(1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one)manufactured by BASF was used as the radical polymerization initiator.

Example 5A

A composition of Example 5A was obtained in an amount of 100 parts byweight in the same manner as in Example 1A except that 2.5 parts byweight of DAROCURE (registered trademark) 1173(2-hydroxy-2-methyl-1-phenyl-propane-1-one) manufactured by BASF wasused as the radical polymerization initiator.

Example 6A

A composition of Example 6A was obtained in an amount of 100 parts byweight in the same manner as in Example 1A except that 71.6 parts byweight of sodium vinyl sulfonate (35 wt % aqueous solution,number-average molecular weight: 130.1) was used as the hydrophiliccompound.

Example 7A

A composition of Example 7A was obtained in an amount of 100 parts byweight in the same manner as in Example 1A except that 25.0 parts byweight of 2-sodium sulfoethyl methacrylate (100 wt % solid content,number-average molecular weight: 216) was used as the hydrophiliccompound.

Example 8A

A composition of Example 8A was obtained in an amount of 100 parts byweight in the same manner as in Example 1A except that 25.0 parts byweight of sodium allyl sulfonate (100 wt % solid content, number-averagemolecular weight: 144.1) was used as the hydrophilic compound.

Example 9A

A composition of Example 9A was obtained in an amount of 100 parts byweight in the same manner as in Example 1A except that 25.0 parts byweight of sodium p-styrene sulfonate (100 wt % solid content,number-average molecular weight: 206) was used as the hydrophiliccompound.

Example 10A

A composition of Example 10A was obtained in an amount of 100 parts byweight in the same manner as in Example 1A except that 50.0 parts byweight of sodium sulfonate-containing urethane acrylate (50.0 wt %solution, number-average molecular weight: 288), which was obtained inSynthesis Example 1, was used as the hydrophilic compound.

Example 11A

A composition of Example 11A was obtained in an amount of 100 parts byweight in the same manner as in Example 1A except that 25.0 parts byweight of sodium 3-mercapto-1-propane sulfonate (100 wt % solid content,number-average molecular weight: 178.2) was used as the hydrophiliccompound.

Example 12A

A composition of Example 12A was obtained in an amount of 100 parts byweight in the same manner as in Example 1A except that 25.0 parts byweight of N-t-butylacrylamide sulfonic acid (100 wt % solid content,number-average molecular weight: 207) was used as the hydrophiliccompound.

Examples 13A to 18A

Compositions of Examples 13A to 18A were obtained in an amount of 100parts by weight in the same manner as in Example 1A except that 25.0parts by weight of dimethyl sulfoxide, 25.0 parts by weight of glycerin,25.0 parts by weight of sucrose, 35.0 parts by weight of aqueous sodiumcarboxymethyl cellulose solution (Adjustment Example 1, 30.0 wt %aqueous solution of Cellogen WS-C manufactured by Dai-ichi Kogyo SeiyakuCo., Ltd.), 35.0 parts by weight of polyvinylpyrrolidone (30.0 wt %solution, Pitts call K-30L manufactured by Dai-ichi Kogyo Seiyaku Co.,Ltd.), and 25.0 parts by weight of sodium hydrogen carbonate wererespectively used as the compatibilizer.

Example 19A

A composition of Example 19A was obtained in an amount of 100 parts byweight in the same manner as in Example 1A except that 50.0 parts byweight of potassium N-t-butyl acrylamide sulfonate (50 wt % aqueoussolution, number-average molecular weight: 245.1) obtained in SynthesisExample 2 was used as the hydrophilic compound.

Examples 20A to 23A

Compositions of Examples 20A to 23A were obtained in an amount of 100parts by weight in the same manner as in Example 1A for reaction withthe primer layers 2A to 5A.

Example 24A

In a state in which the primer layers 1A to 5A were not provided, 20parts of A solution was prepared in advance as follows. 0.5 parts byweight of 3-acryloxypropyltrimethoxysilane as the silane coupling agentcontaining the radical reactive functional group, and 19.5 parts byweight of 1-methoxy-2-propanol as the solvent were uniformly mixed. Inaddition, 80 parts of B solution was separately prepared as follows.14.4 parts by weight of ion exchanged water and 10 parts by weight ofurea were mixed and stirred until the urea was dissolved, and 50.0 partsby weight of sodium N-t-butyl acrylamide sulfonate (50 wt % aqueoussolution, number-average molecular weight: 229), 5.0 parts by weight ofIRGACURE (registered trademark) 500 (a mixture of1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) manufactured byBASF, and 0.6 parts by weight of 3% hydrochloric acid aqueous solutionfor hydrolysis of the silane coupling agent were added to the resultantmixture. This mixture was stirred until a transparent uniform solutionwas obtained. Immediately before application to an object to be coated,the A solution and the B solution were uniformly mixed, therebyobtaining a composition of Example 24A in an amount of 100 parts byweight.

Comparative Example 1A

A composition of Comparative Example 1A was obtained in an amount of 100parts by weight in the same manner as in Example 1A except that urea asthe compatibilizer was not added.

Comparative Example 2A

A composition of Comparative Example 2A was obtained in an amount of 100parts by weight in the same manner as in Example 1A except that IRGACURE(registered trademark) 500 as the radical polymerization initiator wasnot added.

Comparative Example 3A

A composition of Comparative Example 3A was obtained in an amount of 100parts by weight in the same manner as in Example 1A except that 25.0parts by weight of w-carboxy-polycaprolactone (n≈2) monoacrylate (100 wt% liquid, M-5300 manufactured by Toagosei Co., Ltd.) was used as thehydrophilic compound.

Comparative Example 4A

A composition of Comparative Example 4A was obtained in an amount of 100parts by weight in the same manner as in Example 1A by using 25.0 partsby weight of 2-methacryloyloxy ethyl acid phosphate (100 wt % liquid,Light Ester P-1M manufactured by Kyoeisha Chemical Co., Ltd.) as thehydrophilic compound.

Comparative Example 5A

A composition of Comparative Example 5A was obtained in an amount of 100parts by weight in the same manner as in Example 1A except that 25.0parts by weight of dimethylaminopropyl acrylamide methyl chloridequarternary salt (100 wt % liquid, DMAPAA-Q (registered trademark),manufactured by KJ Chemicals Corporation) was used as the hydrophiliccompound.

Comparative Example 6A

A composition of Comparative Example 6A was obtained in an amount of 100parts by weight in the same manner as Example 1A except that 25.0 partsby weight of alkoxypolyethyleneglycol methacrylate (100 wt % liquid,Antox LMA-27 manufactured by Nippon Nyukazai Co., Ltd.) was used as thehydrophilic compound.

Comparative Example 7A

A composition of Comparative Example 7A was obtained in an amount of 100parts by weight in the same manner as in Example 1A by using 25.0 partsby weight of hydroxyethyl acrylate (100 wt % liquid, Light Ester HOA(N)manufactured by Kyoeisha Chemical Co., Ltd.) as the hydrophiliccompound.

Comparative Example 8A

A composition of Comparative Example 8A was obtained in an amount of 100parts by weight in the same manner as in Example 1A by using 25.0 partsby weight of tetrahydrofurfuryl acrylate (100 wt % liquid, LightAcrylate THF-A manufactured by Kyoeisha Chemical Co., Ltd.) as thehydrophilic compound.

Comparative Example 9A

A composition of Comparative Example 9A was obtained in an amount of 100parts by weight in the same manner as in Example 1A by using 25.0 partsby weight of N-vinyl-2-pyrrolidone (100 wt % liquid, N-vinylpyrrolidonemanufactured by NIPPON SHOKUBAI CO., LTD.) as the hydrophilic compound.

Comparative Example 10A

A composition of Comparative Example 10A was obtained in an amount of100 parts by weight in the same manner as in Example 1A except that 25.0parts by weight of ammonium polyoxyethylenenonylpropenylphenylethersulfate (100 wt % liquid, Aqualon HS-10 manufactured by Dai-ichi KogyoSeiyaku Co., Ltd.) was used as the hydrophilic compound, and urea wasnot added.

Comparative Example 11A

A composition of Comparative Example 11A was obtained in an amount of100 parts by weight in the same manner as in Example 1A except that 25.0parts by weight of ethoxylated pentaerythritol tetraacrylate (100 wt %liquid, NK Ester ATM-35E manufactured by Shin-Nakamura Chemical Co.,Ltd.) was used as the hydrophilic compound.

Comparative Example 12A

A composition of Comparative Example 12A was obtained in an amount of100 parts by weight in the same manner as in Example 1A except that 50.0parts by weight of calcium N-t-butylacrylamide sulfonate (50 wt %aqueous solution), which was obtained by allowing calcium hydroxide toreact with N-t-butylacrylamide sulfonic acid in the same manner as inSynthesis Example 2, was used as the hydrophilic compound.

The compositions of Examples 1A to 24A and Comparative Examples 1A to12A are shown in Tables 1 to 3.

TABLE 1 Examples 1A 2A 3A 4A 5A 6A 7A 8A Primer layers (1A to 5A) 1A 1A1A 1A 1A 1A 1A 1A Hydrophilic Compound Radical Hydrophilic compound nameor product reactive group name functional group Sodium N-t-butylAcrylamide Sodium  50.0  50.0  50.0  50.0  50.0 acrylamide sulfonatesulfonate Sodium Vinyl Sodium  71.6 vinyl sulfonate sulfonate 2-sodiummethacryloyl Sodium  25.0 sulfoethyl sulfonate methacrylate Sodium allylAllyl Sodium  25.0 sulfonate sulfonate Sodium p-styrene Styryl Sodiumsulfonate Sodium Acryloyl Sodium sulfonate- sulfonate containingurethane acrylate *1 N-t-butyl-acrylamide Acrylamide Sulfonic sulfonicacid acid Sodium Mercapto Sodium 3-mercapto- sulfonate 1-propanesulfonate Radical IRUGACURE500   2.5   2.5   2.5   2.5   2.5   2.5polymerization IRUGACURE2959   2.5 initiator DAROCURE1173   2.5Compatibilizer Urea  10.0  10.0  10.0  10.0  10.0  10.0  10.0  10.0Dimethyl sulfoxide Glycerin Sucrose Sodium carboxy- methyl cellulosePolyvinyl pyrrolidone Sodium hydrogen carbonate Solvent Ion exchangedwater  27.5  27.5  27.5  27.5  27.5  5.9  52.5  52.5 Isopropyl alcohol 10.0  10.0  10.0  10.0  10.0  10.0  10.0  10.0 Catalyst 3% hydrochloricacid Coupling agent 3-acryloxypropy- Acryloyl ltrimeth oxysilane Solvent1-methoxy- 2-propanol Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0100.0 Examples 9A 10A 11A 12A 13A 14A 15A Primer layers (1A to 5A) 1A 1A1A 1A 1A 1A 1A Hydrophilic Compound Radical Hydrophilic compound name orreactive group product name functional group Sodium Acrylamide Sodium 50.0  50.0  50.0 N-t-butyl sulfonate acrylamide sulfonate Sodium vinylVinyl Sodium sulfonate sulfonate 2-sodium methacryloyl Sodium sulfoethylsulfonate methacrylate Sodium allyl Allyl Sodium sulfonate sulfonateSodium Styryl Sodium  25.0 p-styrene sulfonate Sodium Acryloyl Sodium 50.0 sulfonate- sulfonate containing urethane acrylate *1 N-t-butyAcrylamide Sulfonic  25.0 lacrylamide acid sulfonic acid Sodium MercaptoSodium  25.0 3-mercapto- sulfonate 1-propane sulfonate RadicalIRUGACURE500   2.5   2.5   2.5   2.5   2.5   2.5   2.5 polymerizationIRUGACURE2959 initiator DAROCURE1173 Compatibilizer Urea  10.0  10.0 10.0  10.0 Dimethyl sulfoxide  25.0 Glycerin  25.0 Sucrose  25.0 Sodiumcarboxymethyl cellulose Polyvinyl pyrrolidone Sodium hydrogen carbonateSolvent Ion exchanged water  52.5  27.5  52.5  52.5  12.5  12.5  12.5Isopropyl alcohol  10.0  10.0  10.0  10.0  10.0  10.0  10.0 Catalyst 3%hydrochloric acid Coupling agent 3-acryloxypropyltrimeth Acryloyloxysilane Solvent 1-methoxy-2-propanol Total 100.0 100.0 100.0 100.0100.0 100.0 100.0 *1: Synthesis Example 1

TABLE 2 Examples 16A 17A 18A 19A 20A 21A 22A 23A 24A Primer layers (1Ato 5A) 1A 1A 1A 1A 2A 3A 4A 5A None Hydrophilic Compound name RadicalHydrophilic compound or product name reactive group functional groupSodium Acrylamide Sodium 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0N-t-butyl sulfonate acrylamide sulfonate Sodium vinyl Vinyl Sodiumsulfonate sulfonate 2-sodium methacryloyl Sodium sulfoethyl sulfonatemethacrylate Sodium allyl Allyl Sodium sulfonate sulfonate Sodium StyrylSodium p-styrene sulfonate sulfonate Sodium Acryloyl Sodiumsulfonate-containing sulfonate urethane acrylate *1 N-t-butylacrylamideAcrylamide Sulfonic sulfonic acid acid Potassium Acrylamide Potassium50.0 N-t-butylacrylamide sulfonate sulfonate *2 Sodium Mercapto Sodium3-mercapto-1- sulfonate propane sulfonate Radical IRUGACURE500 2.5 2.52.5 2.5 2.5 2.5 2.5 2.5 5.0 polymerization IRUGACURE2959 initiatorDAROCURE1173 Compatibilizer Urea 10.0 10.0 10.0 10.0 10.0 10.0 Dimethylsulfoxide Glycerin Sucrose Sodium carboxymethyl cellulose 35.0 Polyvinylpyrrolidone 35.0 Sodium hydrogen carbonate 25.0 Solvent Ion exchangedwater 2.5 2.5 12.5 27.5 27.5 27.5 27.5 27.5 14.4 Isopropyl alcohol 10.010.0 10.0 10.0 10.0 10.0 10.0 10.0 Catalyst 3% hydrochloric acid 0.6Coupling 3-acryloxypropyltrimethoxy Acryloyl 0.5 agent silane Solvent1-methoxy-2-propanol 19.5 Total 100.0 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 *1: Synthesis Example 1 *2: Synthesis Example 2

TABLE 3 Comparative Examples 1A 2A 3A 4A 5A 6A 7A 8A 9A 10A 11A 12APrimer layers (1A to 5A) 1A 1A 1A 1A 1A 1A 1A 1A 1A 1A 1A 1A HydrophilicCompound Radical Hydrophilic compound name or reactive group productname functional group Sodium Acrylamide Sodium 50.0 50.0 N-t-butylsulfonate acrylamide sulfonate ω-carboxy- Acryloyl Carboxylic 25.0 poly-acid carprolactone monoacrylate 2-Metha- metha- Phosphoric 25.0cryloyloxy cryloyl acid ethyl acid phosphate Dimethyl- Acrylamide Methyl25.0 aminopropyl chloride acrylamide quarternary methyl amine saltchloride quarternary salt Alkoxypoly- metha- Polyethylene 25.0ethyleneglycol cryloyl chain methacrylate Hydroxyethyl Acryloyl Hydroxyl25.0 acrylate group Tetrahydro- Acryloyl Tetra- 25.0 furfuryl hydrofuranacrylate N-vinyl-2- Vinyl Pyr- 25.0 pyrrolidone rolidone AmmoniumPropenyl Am- 25.0 polyoxyethyl- monium enenonyl- sulfonate propenyl-phenyl- ether sulfate Ethoxylated Acryloyl Poly- 25.0 pentaerythritolethylene tetraacryate chain Calcium Acrylamide Calcium 50.0 N-t-butyl-sulfonate acrylamide sulfonate Radical IRUGACURE500 2.5 2.5 2.5 2.5 2.52.5 2.5 2.5 2.5 2.5 2.5 poly- IRUGACURE2959 merization DAROCURE1173initiator Com- Urea 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 0.0 10.010.0 patibilizer Dimethyl sulfoxide Solvent Ion exchanged water 37.530.0 52.5 52.5 52.5 52.5 52.5 52.5 52.5 62.5 52.5 27.5 Isopropyl alcohol10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Catalyst 3%hydrochloric acid Coupling 3-acryl- Acryloyl agent oxypropyl- trimeth-oxysilane Solvent 1-methoxy-2-propanol Total 100.0 100.0 100.0 100.0100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

Each of the compositions was applied to each of the primer layers 1A to5A, which were formed with respect to crockery that contains siliconoxide in a surface thereof, as illustrated in Table 1 to Table 3, andthe composition was dried using an electric oven at 60° C. for 30minutes and was left stationary at room temperature for 30 minutes.Then, irradiation with ultraviolet rays was performed by using ahigh-pressure mercury lamp with energy of 1000 mJ/cm² as an integral oflight to form a coated film in Examples other than Example 2A andExample 3A. With regard to the composition of Example 12A, afterperforming irradiation with ultraviolet rays, cotton fabric immersed in5 wt % sodium hydroxide aqueous solution was applied to the coated film,and the coated film was washed with water after 5 minutes to neutralizea sulfonic acid group that is a hydrophilic group into sodium sulfonate.With regard to Example 2A, a coated film was formed by using a metalhalide lamp, and with regard to Example 3A, a coated film was formed byusing an ultraviolet LED lamp having a peak light-emitting wavelength of365 nm. In addition, in Example 24A, the primer layers 1A to 5A were notprovided. The A solution and the B solution were blended. Afterapplication of the resultant blended solution, drying was performed inthe same manner as in the method, and irradiation with ultraviolet rayswas performed by using a high-pressure mercury lamp to form a coatedfilm.

On the assumption that the coated film was formed with respect tocrockery such as a toilet bowl and a washstand which are installed at awater-using site, durability of the coated film when being washed with awashing agent, and washability of the coated film with respect to anorganic material such as oil and fat as a contaminant, and an inorganicmaterial were evaluated by the following method.

As a standard for evaluation of the durability of the coated film thatwas formed, a contact angle of a water droplet with respect to a surfaceof the coated film was used in conformity to JIS R 3257 “Testing methodof wettability of glass substrate” (a static drop method was used as atype of the testing method). Specifically, with regard to measurement ofa contact angle of a water droplet, DSA20E manufactured by KRUSS wasused. 4 μL of distilled water was added dropwise to the coated film, anda contact angle after 60 seconds was measured. This method uses thefollowing phenomenon. Specifically, when a physical or chemicalvariation occurs in the coated film formed after being subjected to aphysical or chemical treatment, the contact angle of the water dropletvaries. A state, in which the coated film was not subjected to anytreatment, pertains to “initial”. A treatment, in which the coated filmwas immersed in ion exchanged water maintained at 40° C. for 240 hours,pertains to “water resistance”. A treatment, in which a flushable toiletbrush manufactured by Johnson Company, Limited was reciprocated 1000times under a load of 500 gf in water maintained at 20 to 25° C.,pertains to “abrasion resistance”. A treatment, in which the coated filmwas immersed in Sanpore (registered trademark, manufactured by DainihonJochugiku Co., Ltd.) maintained at 40° C. for 24 hours, pertains to“detergent resistance (acidic)”. A treatment, in which the coated filmwas immersed in Toilet Magic Lynn (registered trademark, manufactured byKao Corporation) maintained at 40° C. for 24 hours, pertains to“detergent resistance (neutral)”. A treatment, in which the coated filmwas immersed in Kabi Killer (registered trademark, manufactured byJohnson Company, Limited) maintained at 40° C. for 24 hours, pertains to“detergent resistance (alkaline)”. The contact angle of the waterdroplet was measured with respect to the respective treatments, andevaluation was made as follows. A case where the contact angle of thewater droplet was 10° or less was evaluated as “A”. A case where thecontact angle of the water droplet was greater than 10° and equal to orless than 20° was evaluated as “B”. A case where the contact angle wasgreater than 20° and equal to or less than 40° was evaluated as “C”. Acase where the contact angle was greater than 40° was evaluated as “D”.“A”, “B”, and “C” were determined as “passing”, and “D” was determinedas “failing”.

As a standard for evaluation of washability of the coated film that wasformed, washability with respect to an organic material such as oil andfat, and washability with respect to an inorganic material wereevaluated, respectively. With regard to removability of the organicmaterial such as oil and fat, oleic acid that is typically used in foodswas used, and evaluation was made as to “oleic acid removability”.Specifically, 300 μL of oleic acid was added dropwise to the coated filmand was immersed in water in a quiet manner, and then time taken foroleic acid to float from a surface of the coated film was measured. Acase where the time taken for the oleic acid to float from the surfaceof the coated film was 30 seconds or less was evaluated as “A”, a casewhere the time was greater than 30 seconds and equal to or less than 60seconds was evaluated as “B”, a case where the time was greater than 60seconds and equal to or less than 120 seconds was evaluated as “C”, anda case where the time was greater than 120 seconds was evaluated as “D”.“A”, “B”, and “C” were determined as “passing”, and “D” was determinedas “failing”.

In addition, with regard to the washability with respect to theinorganic material, Evian (registered trademark), which is hard watercontaining calcium and magnesium in a predetermined amount or more, wasused, and evaluation was made as to “mineral removability”.Specifically, 500 μL of hard water was added dropwise to the coatedfilm, and the coated film was dried at 40° C. for 24 hours to form awhite water droplet spot, and a flushable toilet brush manufactured byJohnson Company, Limited was reciprocated 10 or 20 times under a load of500 gf in water maintained at 20 to 25° C. Then, a remaining waterdroplet spot was observed through visual observation. In washing withthe brush, a case where the water droplet spot was not seen after 10times of reciprocation was evaluated as “A”, a case where the waterdroplet spot was not seen after 20 times of reciprocation was evaluatedas “B”, a case where the water droplet spot was slightly seen after 20times of reciprocation was evaluated as “C”, and a case where the waterdroplet spot was clearly seen after 20 times of reciprocation wasevaluated as “D”. “A”, “B”, and “C” were determined as “passing”, and“D” was determined as “failing”.

The durability and the washability were measured as described above, andcollective results for each of Examples and Comparative Examples areshown in Table 4 to Table 6. An example in which an evaluation result of“D” was not present was determined as “marketability is sufficient”, andan example in which the evaluation result of “D” was present wasdetermined as “marketability is deficient”.

TABLE 4 Examples 1A 2A 3A 4A 5A 6A 7A 8A 9A 10A 11A 12A 13A 14A 15AReaction Irrad- High- O O O O O O O O O O O O O means iation pressurewith mercury lamp O ultra- Metal halide violet lamp rays Ultraviolet OLED lamp Post- Neutralization O treatment Treatment Eval- Dur- Initial AA A A A A A A A A A A A A A uation ability Water B B B B B B C B B B B BB B B resistance Abrasion B B B B B B B B B C B B B B B resistanceDetergent B B B B B B C B B B B B B B B resistance (acidic) Detergent AA A A A A A A A A A A A A A resistance (neutral) Detergent B B B B B B BB B B B B B B B resistance (alkaline) Wash- Oleic acid B B B A A A A A BC B B B B B ability removability Mineral B B B A A A A A B B B B B B Bremovability

TABLE 5 Examples 16A 17A 18A 19A 20A 21A 22A 23A 24A ReactionIrradiation with High-pressure O O O O O O O O O means ultraviolet raysmercury lamp Metal halide lamp Ultraviolet LED lamp Post-treatmentNeutralization Treatment Evaluation Durability Initial A A A A A A A A BWater resistance B B B B B B B B B Abrasion resistance B B B B B B B B CDetergent resistance (acidic) B B B B B B B B B Detergent resistance(neutral) A A A A A A A A B Detergent resistance (alkaline) B B B B B BB B B Washability Oleic acid removability B B B B B B B B C Mineralremovability B B B B B B B B C

TABLE 6 Comparative Examples 1A 2A 3A 4A 5A 6A 7A 8A 9A 10A 11A 12AReaction Irradiation High-pressure mercury O O O O O O O O O O O O meanswith lamp ultraviolet Metal halide lamp rays Ultraviolet LED lampPost-treatment Neutralization Treatment Evaluation Durability Initial DD B B A B C B A A B A Water resistance D D B B C B C B B C D B Abrasionresistance D D B B B C C C B B D B Detergent resistance (acidic) D D D CD B C C C D D C Detergent resistance (neutral) D D C B D B C B B D D BDetergent resistance (alkaline) D D B B D D C B C D D C WashabilityOleic acid removability D D D D D D D D D D D B Mineral removability C CD D D B D D D B D D

Examples 25A and 26A

The following compositions were obtained for reaction with the primerlayer 1A. Specifically, 27.5 parts by weight of ion exchanged water and10 parts by weight of urea were mixed and stirred until the urea wasdissolved. Then, 50.0 parts by weight of sodium N-t-butylacrylamidesulfonate (50 wt % aqueous solution, number-average molecular weight:229), 2.5 parts by weight of sodium persulfate, and 10.0 parts by weightof isopropyl alcohol were added to the resultant mixture, and thismixture was stirred until a transparent uniform solution was obtained,thereby obtaining compositions of Examples 25A and 26A in an amount of100 parts by weight.

Example 27A

A composition of Example 27A was obtained in an amount of 100 parts byweight in the same manner as Example 25A except that 2.5 parts by weightof V-50 (2,2′ -azobis(propane-2-carboamidine)dihydrochloride,manufactured by Wako Pure Chemical Industries, Ltd.) was used as theradical polymerization initiator.

Example 28A

A composition of Example 28A was obtained in an amount of 100 parts byweight in the same manner as Example 25A except that 5.0 parts by weightof Perhexyl PV-50E (emulsion of t-hexylperoxy pivalate, effectivecomponent: 50% by weight manufactured by NOF CORPORATION) was used asthe radical polymerization initiator.

Example 29A

A composition of Example 29A was obtained in an amount of 100 parts byweight in the same manner as in Example 25A except that 71.6 parts byweight of sodium vinyl sulfonate (35 wt % aqueous solution,number-average molecular weight: 130.1) was used as the hydrophiliccompound.

Example 30A

A composition of Example 30A was obtained in an amount of 100 parts byweight in the same manner as in Example 25A except that 25.0 parts byweight of 2-sodium sulfoethyl methacrylate (100 wt % solid content,number-average molecular weight: 216) was used as the hydrophiliccompound.

Example 31A

A composition of Example 31A was obtained in an amount of 100 parts byweight in the same manner as in Example 25A except that 25.0 parts byweight of sodium allyl sulfonate (100 wt % solid content, number-averagemolecular weight: 144.1) was used as the hydrophilic compound.

Example 32A

A composition of Example 32A was obtained in an amount of 100 parts byweight in the same manner as in Example 25A except that 25.0 parts byweight of sodium p-styrene sulfonate (100 wt % solid content,number-average molecular weight: 206) was used as the hydrophiliccompound.

Example 33A

A composition of Example 33A was obtained in an amount of 100 parts byweight in the same manner as in Example 25A except that 50.0 parts byweight of sodium sulfonate-containing urethane acrylate (50.0 wt %solution, number-average molecular weight: 288), which was obtained inSynthesis Example 1, was used as the hydrophilic compound.

Example 34A

A composition of Example 34A was obtained in an amount of 100 parts byweight in the same manner as in Example 25A except that 25.0 parts byweight of sodium 3-mercapto-1-propane sulfonate (100 wt % solid content,number-average molecular weight: 178.2) was used as the hydrophiliccompound.

Example 35A

A composition of Example 35A was obtained in an amount of 100 parts byweight in the same manner as in Example 25A except that 25.0 parts byweight of N-t-butylacrylamide sulfonic acid (100 wt % solid content,number-average molecular weight: 207) was used as the hydrophiliccompound.

Examples 36A to 41A

Compositions of Examples 36A to 41A were obtained in an amount of 100parts by weight in the same manner as in Example 25A except that 25.0parts by weight of dimethyl sulfoxide, 25.0 parts by weight of glycerin,25.0 parts by weight of sucrose, 35.0 parts by weight of aqueous sodiumcarboxymethyl cellulose solution (Adjustment Example 1, 30.0 wt %aqueous solution of Cellogen WS-C manufactured by Dai-ichi Kogyo SeiyakuCo., Ltd.), 35.0 parts by weight of aqueous polyvinylpyrrolidonesolution (30.0 wt % solution, Pitts call K-30L manufactured by Dai-ichiKogyo Seiyaku Co., Ltd.), and 25.0 parts by weight of sodium hydrogencarbonate are respectively used as the compatibilizer.

Example 42A

A composition of Example 42A was obtained in an amount of 100 parts byweight in the same manner as in Example 25A except that 50.0 parts byweight of potassium N-t-butyl acrylamide sulfonate (50 wt % aqueoussolution, number-average molecular weight: 245.1) obtained in SynthesisExample 2 was used as the hydrophilic compound.

Examples 43A to 46A

Compositions of Examples 43A to 46A were obtained in an amount of 100parts by weight in the same manner as in Example 25A for reaction withthe primer layers 2A to 5A.

Example 47A

In a state in which the primer layers 1A to 5A were not provided, 20parts of A solution was prepared in advance as follows. 0.5 parts byweight of 3-acryloxypropyltrimethoxysilane as the silane coupling agentcontaining the radical reactive functional group, and 19.5 parts byweight of 1-methoxy-2-propanol as the solvent were uniformly mixed. Inaddition, 80 parts of C solution was separately prepared as follows.14.4 parts by weight of ion exchanged water and 10 parts by weight ofurea were mixed and stirred until the urea was dissolved, 50.0 parts byweight of sodium N-t-butyl acrylamide sulfonate (50 wt % aqueoussolution, number-average molecular weight: 229), 5.0 parts by weight ofsodium persulfate, and 0.6 parts by weight of 3% hydrochloric acidaqueous solution for hydrolysis of the silane coupling agent were addedto the resultant mixture. This mixture was stirred until a transparentuniform solution was obtained. Immediately before application to anobject to be coated, the A solution and the C solution were uniformlymixed, thereby obtaining a composition of Example 47A in an amount of100 parts by weight.

Comparative Example 13A

A composition of Comparative Example 13A was obtained in an amount of100 parts by weight in the same manner as in Example 25A except thaturea as the compatibilizer was not added.

Comparative Example 14A

A composition of Comparative Example 14A was obtained in an amount of100 parts by weight in the same manner as in Example 25A except thatsodium persulfate as the radical polymerization initiator was not added.

Comparative Example 15A

A composition of Comparative Example 15A was obtained in an amount of100 parts by weight in the same manner as in Example 25A except that25.0 parts by weight of w-carboxy-polycaprolactone (11=2) monoacrylate(100 wt % liquid, M-5300 manufactured by Toagosei Co., Ltd.) was used asthe hydrophilic compound.

Comparative Example 16A

A composition of Comparative Example 16A was obtained in an amount of100 parts by weight in the same manner as in Example 25A by using 25.0parts by weight of 2-methacryloyloxy ethyl acid phosphate (100 wt %liquid, Light Ester P-1M manufactured by Kyoeisha Chemical Co., Ltd.) asthe hydrophilic compound.

Comparative Example 17A

A composition of Comparative Example 17A was obtained in an amount of100 parts by weight in the same manner as in Example 25A except that25.0 parts by weight of dimethylaminopropyl acrylamide methyl chloridequarternary salt (100 wt % liquid, DMAPAA-Q (registered trademark)manufactured by KJ Chemicals Corporation) was used as the hydrophiliccompound.

Comparative Example 18A

A composition of Comparative Example 18A was obtained in an amount of100 parts by weight in the same manner as Example 25A except that 25.0parts by weight of alkoxypolyethyleneglycol methacrylate (100 wt %liquid, Antoxy LMA-27 manufactured by Nippon Nyukazai Co., Ltd.) wasused as the hydrophilic compound.

Comparative Example 19A

A composition of Comparative Example 19A was obtained in an amount of100 parts by weight in the same manner as in Example 25A by using 25.0parts by weight of hydroxyethyl acrylate (100 wt % liquid, Light EsterHOA(N) manufactured by Kyoeisha Chemical Co., Ltd.) as the hydrophiliccompound.

Comparative Example 20A

A composition of Comparative Example 20A was obtained in an amount of100 parts by weight in the same manner as in Example 25A by using 25.0parts by weight of tetrahydrofurfuryl acrylate (100 wt % liquid, LightAcrylate THF-A manufactured by Kyoeisha Chemical Co., Ltd.) as thehydrophilic compound.

Comparative Example 21A

A composition of Comparative Example 21A was obtained in an amount of100 parts by weight in the same manner as in Example 25A by using 25.0parts by weight of N-vinyl-2-pyrrolidone (100 wt % liquid,N-vinylpyrrolidone manufactured by NIPPON SHOKUBAI CO., LTD.) as thehydrophilic compound.

Comparative Example 22A

A composition of Comparative Example 22A was obtained in an amount of100 parts by weight in the same manner as in Example 25A except that25.0 parts by weight of ammonium polyoxyethylenenonylpropenylphenylethersulfate (100 wt % liquid, Aqualon HS-10 manufactured by Dai-ichi KogyoSeiyaku Co., Ltd.) was used as the hydrophilic compound.

Comparative Example 23A

A composition of Comparative Example 23A was obtained in an amount of100 parts by weight in the same manner as in Example 25A except that25.0 parts by weight of ethoxylated pentaerythritol tetraacrylate (100wt % liquid, NK Ester ATM-35E manufactured by Shin-Nakamura ChemicalCo., Ltd.) was used as the hydrophilic compound.

Comparative Example 24A

A composition of Comparative Example 24A was obtained in an amount of100 parts by weight in the same manner as in Example 25A except that50.0 parts by weight of calcium N-t-butylacrylamide sulfonate (50 wt %aqueous solution), which was obtained by allowing calcium hydroxide toreact with N-t-butylacrylamide sulfonic acid in the same manner as inSynthesis Example 2, was used as the hydrophilic compound.

The compositions of Examples 25A to 47A and Comparative Examples 13A to24A were shown in Tables 7 to 9.

TABLE 7 Examples 25A 26A 27A 28A 29A 30A 31A 32A 33A 34A 35A 36A 37A 38APrimer layers (1A to 5A) 1A 1A 1A 1A 1A 1A 1A 1A 1A 1A 1A 1A 1A 1AHydro- Compound Radical Hydro- philic name or reactive philic com-product func- group pound name tional group Sodium N- Acryl- Sodium 50.050.0 50.0 50.0 50.0 50.0 50.0 t-butyl amide sul- acrylamide fonatesulfonate Sodium vinyl Vinyl Sodium 71.6 sulfonate sul- fonate 2-sodiummetha- Sodium 25.0 sulfoethyl cryloyl sul- methacrylate fonate Sodiumallyl Allyl Sodium 25.0 sul- sul- fonate fonate Sodium Styryl Sodium25.0 p-styrene sul- sulfonate fonate Sodium Acryloyl Sodium 50.0sulfonate- sul- containing fonate urethane acrylate *1 N-t-butyl- Acryl-Sulfonic 25.0 acrylamide amide acid sulfonic acid Sodium Mercapto Sodium25.0 3-mercapto- sul- propane fonate sulfonate Radical Sodium persulfate2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 poly- V-50 2.5 meri-Perhexyl PV-50E 5.0 zation initiator Compat- Urea 10.0 10.0 10.0 10.010.0 10.0 10.0 10.0 10.0 10.0 10.0 ibilizer Dimethyl sulfoxide 25.0Glycerin 25.0 Sucrose 25.0 Sodium carboxymethyl cellulose Polyvinylpyrrolidone Sodium hydrogen carbonate Solvent Ion exchanged water 27.527.5 27.5 25.0 5.9 52.5 52.5 52.5 27.5 52.5 52.5 12.5 12.5 12.5Isopropyl alcohol 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.010.0 10.0 10.0 Catalyst 3% hydrochloric acid Coupling 3-acryloxy-Acryloyl agent propyl- trimethoxy silane Solvent 1-methoxy-2-propanolTotal 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 *1: Synthesis Example

TABLE 8 Examples 39A 40A 41A 42A 43A 44A 45A 46A 47A Primer layers (1Ato 5A) 1A 1A 1A 1A 2A 3A 4A 5A None Hydrophilic Compound name RadicalHydrophilic compound or product name reactive group functional groupSodium N-t-butyl Acrylamide Sodium 50.0 50.0 50.0 50.0 50.0 50.0 50.050.0 acrylamide sulfonate sulfonate Sodium vinyl Vinyl Sodium sulfonatesulfonate 2-sodium sulfoethyl methacryloyl Sodium methacrylate sulfonateSodium allyl Allyl Sodium sulfonate sulfonate Sodium p-styrene StyrylSodium sulfonate sulfonate Sodium sulfonate- Acryloyl Sodium containingurethane sulfonate acrylate *1 N-t-butylacrylamide Acrylamide Sulfonicacid sulfonic acid Potassium Acrylamide Potassium 50.0N-t-butylacrylamide sulfonate sulfonate *2 Sodium Mercapto Sodium3-mercapto-1- sulfonate propane sulfonate Radical Sodium persulfate 2.52.5 2.5 2.5 2.5 2.5 2.5 2.5 5.0 polymerization V-50 initiator PerhexylPV-50E Compatibilizer Urea 10.0 10.0 10.0 10.0 10.0 10.0 Dimethylsulfoxide Glycerin Sucrose Sodium carboxymethyl cellulose 35.0 Polyvinylpyrrolidone 35.0 Sodium hydrogen carbonate 25.0 Solvent Ion exchangedwater 2.5 2.5 12.5 27.5 27.5 27.5 27.5 27.5 14.4 Isopropyl alcohol 10.010.0 10.0 10.0 10.0 10.0 10.0 10.0 Catalyst 3% hydrochloric acid 0.6Coupling 3 -acryloxypropyl- Acryloyl 0.5 agent trimethoxy silane Solvent1-methoxy-2-propanol 19.5 Total 100.0 100.0 100.0 100.0 100.0 100.0100.0 100.0 100 *1: Synthesis Example 1 *2: Synthesis Example 2

TABLE 9 Comparative Examples 13A 14A 15A 16A 17A 18A 19A 20A 21A 22A 23A24A Primer layers (1A to 5A) 1A 1A 1A 1A 1A 1A 1A 1A 1A 1A 1A 1A Hydro-Compound Radical Hydro- philic name or reactive philic com- product namefunctional group pound group Sodium Acryl- Sodium 50.0 50.0 N-t-butylamide sulfonate acrylamide sulfonate ω-carboxy-poly- Acryloyl Carboxylic25.0 caprolactone acid monoacrylate 2-Methacryloyloxy metha- Phosphoric25.0 ethyl acid phosphate cryloyl acid Dimethyl- Acryl- Methyl 25.0aminopropyl amide chloride acrylamide quarternary methyl chloride aminesalt quarternary salt Alkoxypoly- metha- Polyethylene 25.0 ethylene-cryloyl chain glycol methacrylate Hydroxyethyl Acryloyl Hydroxyl 25.0acrylate group Tetrahydro- Acryloyl Tetra- 25.0 furfuryl hydrofuranacrylate N-vinyl-2- Vinyl Pyrrolidone 25.0 pyrrolidone Ammonium PropenylAmmonium 25.0 polyoxy- sulfonate ethylenenonyl- propenyl- phenylethersulfate Ethoxylated Acryloyl Polyethylene 25.0 pentaerythritol chaintetraacrylate (EO 35 moles) Calcium N-t- Acrylamide Calcium 50.0butyl-acrylamide sulfonate sulfonate Radical Sodium persulfate 2.5 2.52.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 poly- V-50 merization PerhexylPV-50E initiator Com- Urea 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.010.0 10.0 patibilizer Dimethyl sulfoxide Solvent Ion exchanged water37.5 30.0 52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5 27.5 Isopropylalcohol 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0Catalyst 3% hydrochloric acid Coupling 3-acryloxypropyl- Acryloyl agenttrimethoxysilane Solvent 1-methoxy-2-propanol Total 100.0 100.0 100.0100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

Each of the compositions was applied to each of the primer layers 1A to5A, which were formed with respect to crockery that contains siliconoxide in a surface thereof, as illustrated in Table 7 to Table 9, anddrying was performed at 120° C. for 30 minutes by using an electric ovenin Examples other than Example 26A to form a coated film. With regard tothe composition of Example 35A, after performing drying at 120° C. for30 minutes by using an electric oven, cotton fabric immersed in 5 wt %sodium hydroxide aqueous solution was applied to the coated film, andthe coated film was washed with water after 5 minutes to neutralize asulfonic acid group that is a hydrophilic group into sodium sulfonate.In Example 26A, irradiation with infrared rays was performed, and dryingwas performed for 30 minutes at a raw material temperature of 120° C. Inaddition, in Example 47A, the primer layers 1A to 5A were not provided.The A solution and the C solution were blended. After application of theresultant blended solution, heating was performed in the same manner asin the method to form a coated film.

Durability and washability were evaluated with respect to the coatedfilm that was formed in the same manner as in the coated film that wasformed with ultraviolet curing. Collective results for each of Examplesand Comparative Examples are shown in Table 10 to Table 12. An examplein which the evaluation result of “D” was not present was determined as“marketability is sufficient”, and an example in which the evaluationresult of “D” was present was determined as “marketability isdeficient”.

TABLE 10 Examples 25A 26A 27A 28A 29A 30A 31A 32A 33A 34A 35A 36A 37A38A Reaction Drying by electric oven O O O O O O O O O O O O O means(120° C., 30 minutes) Drying by irradiation O with infrared rays (120°C., 30 minutes) Post- Neutralization O treatment Treatment EvaluationDurability Initial A A A A A A A A A A A A A A Water B B B B B C B B B BB B B B resistance Abrasion B B B B B B B B C B B B B B resistanceDetergent B B B B B C B B B B B B B B resistance (acidic) Detergent A AA A A A A A A A A A A A resistance (neutral) Detergent B B B B B B B B BB B B B B resistance (alkaline) Wash- Oleic acid B B A A A A A B C B B BB B removability ability Mineral B B A A A A A B B B B B B Bremovability

TABLE 11 Examples 39A 40A 41A 42A 43A 44A 45A 46A 47A Reaction Drying byelectric oven (120° C., 30 minutes) O O O O O O O O O means Drying byirradiation with infrared rays (120° C., 30 minutes) Post-treatmentNeutralization Treatment Evaluation Durability Initial A A A A A A A A BWater resistance B B B B B B B B B Abrasion resistance B B B B B B B B BDetergent resistance (acidic) B B B B B B B B B Detergent resistance(neutral) A A A A A A A A B Detergent resistance (alkaline) B B B B B BB B B Washability Oleic acid removability B B B B B B B B C Mineralremovability B B B B B B B B C

TABLE 12 Comparative Examples 13A 14A 15A 16A 17A 18A 19A 20A 21A 22A23A 24A Reaction Drying by electric oven O O O O O O O O O O O O means(120° C., 30 minutes) Drying by irradiation with infrared rays (120° C.,30 minutes) Post-treatment Neutralization Treatment EvaluationDurability Initial D D B B A B C B A A B A Water resistance D D B B C BC B B C D B Abrasion resistance D D B B B C C C B B D B Detergentresistance D D D C D B C C C D D C (acidic) Detergent resistance D D C BD B C B B D D B (neutral) Detergent resistance D D B B D D C B C D D C(alkaline) Washability Oleic acid removability D D D D D D D D D D D BMineral removability C C D D D B D D D B D D

Hereinafter, a description will be given of Examples 1B to 15B, andComparative Examples 1B to 10B according to the third aspect and thefourth aspect of the invention.

Example 1B

The following composition was obtained for reaction with the primerlayer 1B. Specifically, 30.0 parts by weight of ion exchanged water and10 parts by weight of urea were mixed and stirred until the urea wasdissolved. 50.0 parts by weight of sodium 2-aminoethyl sulfonate (50 wt% aqueous solution, number-average molecular weight: 147.2), and 10.0parts by weight of isopropyl alcohol were added to the resultantmixture, and this mixture was stirred until a transparent uniformsolution was obtained, thereby obtaining a composition of Example 1B inan amount of 100 parts by weight.

Example 2B

A composition of Example 2B was obtained in an amount of 100 parts byweight in the same manner as in Example 1B except that 50.0 parts byweight of potassium 2-aminoethyl sulfonate (50 wt % aqueous solution,number-average molecular weight: 163.3) was used as the hydrophiliccompound.

Examples 3B and 4B

Compositions of Example 3B and 4B were obtained in an amount of 100parts by weight in the same manner as in Example 1B except that 25.0parts by weight of 2-aminoethyl sulfonic acid (50 wt % aqueous solution,number-average molecular weight: 125.2) was used as the hydrophiliccompound.

Examples 5B to 10B

Compositions of Examples 5B to 10B were obtained in an amount of 100parts by weight in the same manner as in Example 1B except that 25.0parts by weight of dimethyl sulfoxide, 25.0 parts by weight of glycerin,10.0 parts by weight of sucrose, 33.3 parts by weight of 30% aqueoussolution of carboxymethyl cellulose sodium, 33.3 parts by weight of 30%aqueous solution of polyvinylpyrolidone, 10.0 parts by weight of sodiumhydrogen carbonate were respectively used as the compatibilizer.

Example 11B

A composition of Example 11B was obtained in an amount of 100 parts byweight in the same manner as in Example 1B except that 62.5 parts byweight of sodium 4-aminobenzene sulfonate (40 wt % aqueous solution,number-average molecular weight: 195.1) was used as the hydrophiliccompound.

Example 12B

A composition of Example 12B was obtained in an amount of 100 parts byweight in the same manner as in Example 1B except that 41.7 parts byweight of sodium 2-hydroxyethyl sulfonate (60 wt % aqueous solution,number-average molecular weight: 148.1) was used as the hydrophiliccompound, and 0.1 parts by weight of tin dibutyl dilaurate was used asthe reaction catalyst.

Example 13B

A composition of Example 13B was obtained in an amount of 100 parts byweight in the same manner as in Example 1B for reaction with respect tothe primer layer 2B.

Example 14B

The following composition was obtained for reaction with the primerlayer 2B. Specifically, a composition of Example 14B was obtained in anamount of 100 parts by weight in the same manner as in Example 1B exceptthat 50.0 parts by weight of sodium 3-mercapto-1-propane sulfonate (50wt % aqueous solution, number-average molecular weight: 178.2) was usedas the hydrophilic compound, and 1.0 parts by weight ofN,N-dimethylbenzylamine was used as the reaction catalyst.

Example 15B

In a state in which the primer layers 1B and 2B were not provided, 20parts of an A solution was prepared in advance as follows. 0.5 parts byweight of 3-isocyanatopropyltrimethoxysilane as the silane couplingagent and 19.5 parts by weight of methanol as the solvent were uniformlymixed. In addition, 80 parts of B solution was separated prepared asfollows. 19.2 parts by weight of methanol and 10 parts by weight of ureawere mixed and stirred until the urea was dissolved, and 50.0 parts byweight of sodium 2-aminoethyl sulfonate (50 wt % aqueous solution,number-average molecular weight: 147.2), and 0.8 parts by weight ofN-methylmorpholine for hydrolysis of the silane coupling agent wereadded to the resultant mixture, and this mixture was stirred until atransparent uniform solution was obtained. Immediately beforeapplication to an object to be coated, the A solution and the B solutionwere uniformly mixed, thereby obtaining a composition of Example 15B inan amount of 100 parts by weight.

Comparative Example 1B

The following composition was obtained for reaction with the primerlayer 1B. Specifically, a composition of Comparative Example 1B wasobtained in an amount of 100 parts by weight in the same manner as inExample 1B except that 62.5 parts by weight of calcium 2-aminoethylsulfonate (40 wt % aqueous solution) was used as the hydrophiliccompound.

Comparative Example 2B

A composition of Comparative Example 2B was obtained in an amount of 100parts by weight in the same manner as in Example 1B except that urea asthe compatibilizer was not added.

Comparative Example 3B

A composition of Comparative Example 3B was obtained in an amount of 100parts by weight in the same manner as in Example 1B except that 62.5parts by weight of sodium glycine (40 wt % aqueous solution) was used asthe hydrophilic compound.

Comparative Example 4B

A composition of Comparative Example 4B was obtained in an amount of 100parts by weight in the same manner as in Example 1B except that 27.8parts by weight of 2-amino-2-methyl-1-propaneol (90 wt % aqueoussolution, AMP-90 manufactured by The Dow Chemical Company) was used asthe hydrophilic compound.

Comparative Example 5B

A composition of Comparative Example 5B was obtained in an amount of 100parts by weight in the same manner as in Example 1B except that 62.5parts by weight of disodium dihydrogen-2-aminoethyl phosphate (40 wt %aqueous solution) was used as the hydrophilic compound.

Comparative Example 6B

A composition of Comparative Example 6B was obtained in an amount of 100parts by weight in the same manner as in Example 1B except that 25.0parts by weight of (2-hydroxyethyl)trimethyl ammonium chloride (40 wt %aqueous solution) was used as the hydrophilic compound.

Comparative Example 7B

A composition of Comparative Example 7B was obtained in an amount of 100parts by weight in the same manner as in Example 1B except that 25.0parts by weight of tetrahydrofurfuryl alcohol (100 wt % liquid) was usedas the hydrophilic compound.

Comparative Example 8B

A composition of Comparative Example 8B was obtained in an amount of 100parts by weight in the same manner as in Example 1B except that 62.5parts by weight of polyoxyethylenelauryl ether (40 wt % aqueoussolution, Cellogen WS-C manufactured by Dai-ichi Kogyo Seiyaku Co.,Ltd.) was used as the hydrophilic compound, and 0.1 parts by weight oftin dibutyl dilaurate was used as the reaction catalyst.

Comparative Example 9B

The following composition was obtained for reaction with the primerlayer 2. Specifically, a composition of Comparative Example 9B wasobtained in an amount of 100 parts by weight in the same manner as inExample 1B except that 89.0 parts by weight of disodiumpolyoxyethylenealkyl sulfosuccinate (25 wt % aqueous solution,NEO-HITENOL S-70 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) wasused as the hydrophilic compound, 1.0 parts by weight ofN,N-dimethylbenzylamine was used as the reaction catalyst, and urea wasnot added.

Comparative Example 10B

In a state in which the primer layer was not provided, a composition ofComparative Example 10B was obtained in an amount of 100 parts by weightin the same manner as in Examples 1B.

Compositions of Examples 1B to 15B, and Comparative Examples 1B to 10Bare shown in Tables 13 and 14.

TABLE 13 Examples 1B 2B 3B 4B 5B 6B 7B 8B 9B Primer layers (1B and 2B)1B 1B 1B 1B 1B 1B 1B 1B 1B Hydro- Compound Reactive Hydro- philic nameor functional philic com- product group group pound name Sodium 2- AminoSodium 50.0 50.0 50.0 50.0 50.0 50.0 aminoethyl group sul- sulfonatefonate Potassium Amino Po- 50.0 2- group tassium aminoethyl sul-sulfonate fonate 2- Amino Sulfonic 25.0 25.0 aminoethyl group acidsulfonic acid Sodium Amino Sodium 4-amino- group sul- benzene fonatesulfonate Sodium Hydroxyl Sodium 2-hydroxy- group sul- ethyl fonate sul-fonate Sodium Mercapto Sodium 3-mercapto- group sul- 1-propane fonatesulfonate Re- Tin dibutyl dilaurate action N,N-dimethylbenzylaminecatalyst Com- Urea 10.0 10.0 10.0 10.0 pati- Dimethyl sulfoxide 25.0bilizer Glycerin 25.0 Sucrose 10.0 30% aqueous solution of sodium 33.3carboxymethyl cellulose 30% aqueous solution of 33.3 polyvinylpyrrolidone Sodium hydrogen carbonate Solvent Ion exchanged water 30.030.0 55.0 55.0 15.0 15.0 30.0 6.7 6.7 Isopropyl alcohol 10.0 10.0 10.010.0 10.0 10.0 10.0 10.0 10.0 Methanol Catalyst N-methylmorpholineCoupling 3-isocynatopropyl isocyanate agent trimethoxy silane SolventMethanol Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0Examples 10B 11B 12B 13B 14B 15 Primer layers (1B and 2B) 1B 1B 1B 2B 2BNone Hydro- Compound Reactive Hydro- philic name func- philic com- orproduct tional group pound name group Sodium 2- Amino Sodium 50.0 50.050.0 aminoethyl group sulfonate sulfonate Potassium Amino Potassium2-aminoethyl group sulfonate sulfonate 2-aminoethyl Amino Sulfonicsulfonic acid group acid Sodium Amino Sodium 62.5 4-amino groupsulfonate benzene sulfonate Sodium Hydroxyl Sodium 41.7 2-hy- groupsulfonate droxyethyl sulfonate Sodium Mercapto Sodium 50.0 3-mercapto-1-group sulfonate propane sulfonate Re- Tin dibutyl 0.1 action dilauratecatalyst N,N-dimethyl- 1.0 benzylamine Com- Urea 10.0 10.0 10.0 10.010.0 pati- Dimethyl bilizer sulfoxide Glycerin Sucrose 30% aqueoussolution of sodium carboxymethyl cellulose 30% aqueous solution ofpolyvinyl pyrrolidone Sodium 10.0 hydrogen carbonate Solvent Ionexchanged water 30.0 17.5 38.2 30.0 29.0 Isopropyl alcohol 10.0 10.010.0 10.0 10.0 Methanol 19.2 Catalyst N-methylmorpholine 0.8 Coupling3-iso- isocyanate 0.5 agent cynatopropyl trimethoxy silane SolventMethanol 19.5 Total 100.0 100.0 100.0 100.0 100.0 100.0

TABLE 14 Comparative Examples 1B 2B 3B 4B 5B 6B 7B 8B 9B 10B Primerlayers (1B to 6B) 1B 1B 1B 1B 1B 1B 1B 1B 2B None Hydro- Compound nameRadical Hydrophilic philic or product name reactive group com-functional pound group Sodium 2- Amino Sodium 50.0 50.0 aminoethyl groupsulfonate sulfonate Calcium 2- Amino Calcium 62.5 aminoethyl groupsulfonate sulfonate sodium glycine Amino Sodium 62.5 group sulfonate2-amino-2- Amino Hydroxyl 27.8 methyl-1-propanol group group disodiumAmino Sodium 62.5 dihydrogen- group phosphate 2-aminoethyl phosphateTetrahydro- Hydroxyl Tetrahydro- 25.0 furfuryl group furfuryl alcoholgroup (2-hydroxyethyl) Hydroxyl Quarternary 25.0 trimethyl groupammonium ammonium salt chloride Poly- Hydroxyl Poly- 62.5oxyethylenelauryl group oxyethylene ether group Disodium Hydroxyl Poly-89.0 polyoxy- group oxyethylene ethylenealkyl group sulfosuccinateReaction Tin dibutyl dilaurate 0.1 catalyst N,N-dimethylbenzylamine 1.0Com- Urea 10.0 10.0 10.0 10.0 10.0 10.0 10.0 pati- Dimethyl sulfoxidebilizer Glycerin Sucrose Sodium carboxymethyl cellulose polyvinylpyrrolidone Sodium hydrogen carbonate Solvent Ion exchanged water 17.540.0 17.5 52.2 17.5 55.0 55.0 27.4 30.0 Isopropyl alcohol 10.0 10.0 10.010.0 10.0 10.0 10.0 10.0 10.0 10.0 Total 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 100.0 100.0

Each of the compositions was applied to each of the primer layers 1B and2B which were formed with respect to crockery that contains siliconoxide in a surface thereof as described in Table 1 and Table 2, and thecrockery was dried at 60° C. for 30 minutes by using an electric ovenand was left stationary at room temperature for 30 minutes. Then,heating was performed at 120° C. for 30 minutes by using an electricoven to form a coated film. With regard to the composition of Example3B, after performing heating, cotton fabric immersed in 5 wt % sodiumhydroxide aqueous solution was applied to the coated film, and thecoated film was washed with water after 5 minutes to neutralize asulfonic acid group that is a hydrophilic group into sodium sulfonate.In addition, in Example 15B, the primer layers 1B and 2B were notprovided. The A solution and the B solution were blended. Afterapplication of the resultant blended solution, drying and heating wereperformed in the same manner as in the method to form a coated film.

On the assumption that the coated film was formed with respect tocrockery such as a toilet bowl and a washstand which are installed at awater-using site in a building, and the like, durability of the coatedfilm when being washed with a washing agent, and washability of thecoated film with respect to an organic material such as oil and fat as acontaminant, and an inorganic material were evaluated by the followingmethod.

The durability of the coated film that was formed was evaluated by thesame method and standard as in Examples of the first aspect and thesecond aspect.

The washability of the coated film that was formed was evaluated by thesame method and standard as Examples of the first aspect and the secondaspect.

The washability with respect to an inorganic material was evaluated bythe same method and standard as in Examples of the first aspect and thesecond aspect.

The durability and the washability were measured as described above, andcollective results of each of Examples and Comparative Examples areshown in Tables 15 and 16. An example in which the evaluation result of“D” was not present was determined as “marketability is sufficient”, andan example in which the evaluation result of “D” was present wasdetermined as “marketability is deficient”.

TABLE 15 Examples 1B 2B 3B 4B 5B 6B 7B 8B 9B 10B 11B 12B 13B 14B 15BReaction Heating O O O O O O O O O O O O O O O means Post-treatmentNeutralization Treatment O Evaluation Durability Initial A A A A A A A AA A A A A A B Water resistance B B B B B B B B B B B B B B B Abrasionresistance B B B B B B B B B B B B B B B Detergent resistance B B B B BB B B B B B B B B B (acidic) Detergent resistance A A B B B B B B B B AA B A B (neutral) Detergent resistance B B B B B B B B B B B B B B B(alkaline) Washability Oleic acid removability B B B B B B B B B B B B BB C Mineral removability B B B B B B B B B B B B B B C

TABLE 16 Comparative Examples 1B 2B 3B 4B 5B 6B 7B 8B 9B 10B ReactionHeating O O O O O O O O O O means Neutralization Treatment Post- treatment Evaluation Durability Initial A D C D B C C B B D Water resistanceB D C D B C C B B D Abrasion resistance B D D D B C C B B D Detergentresistance (acidic) D D C D D D D D D D Detergent resistance (neutral) CD C D D D D D D D Detergent resistance (alkaline) B D D D D C C D D DWashability Oleic acid removability D D D D D D D D D D Mineralremovability D D D D D D D C C D

1. A hydrophilic treatment coating composition comprising: a hydrophiliccompound that contains a radical reactive functional group and an alkalimetal salt of a sulfonic acid group, does not contain a hydrophilicportion at a site other than an end of a molecular chain, and does notcontain a branched chain; a radical polymerization initiator; and apolar compatibilizer, wherein the polar compatibilizer is at least onemember selected from the group consisting of urea, melamine, acryloylmorpholine, dimethyl acrylamide, hydroxyethyl acrylamide, acetonitrile,N,N-dimethylformamide, ethylene glycol, glycerin, trimethylolpropane,ditrimethylolpropane, erythritol, dipentaerythritol, triose, tetrose,pentose, hexose, sedoheptulose, glucose, maltose, sucrose, lactose,cellobiose, raffinose, acarbose, oligosaccharides, cyclodextrin,dextrin, starch, sodium carboxymethyl cellulose, polyvinyl pyrrolidone,sodium polyacrylate, sodium hydrogen carbonate, sodium carbonate, sodiumhydrogen sulfate, and sodium sulfate.
 2. A hydrophilic treatment coatingcomposition comprising: a silane coupling agent that contains a radicalreactive functional group; a hydrophilic compound that contains aradical reactive functional group and an alkali metal salt of a sulfonicacid group, does not contain a hydrophilic portion at a site other thanan end of a molecular chain, and does not contain a branched chain; aradical polymerization initiator; and a polar compatibilizer, whereinthe polar compatibilizer is at least one member selected from the groupconsisting of urea, melamine, acryloyl morpholine, dimethyl acrylamide,dimethylaminopropyl acrylamide, isopropyl acrylamide, diethylacrylamide, hydroxyethyl acrylamide, dimethyl sulfoxide, acetonitrile,N,N-dimethylformamide, ethylene glycol, glycerin, trimethylolpropane,ditrimethylolpropane, erythritol, dipentaerythritol, triose, tetrose,pentose, hexose, sedoheptulose, glucose, maltose, sucrose, lactose,cellobiose, raffinose, acarbose, oligosaccharides, cyclodextrin,dextrin, starch, sodium carboxymethyl cellulose, polyvinyl pyrrolidone,sodium polyacrylate, sodium hydrogen carbonate, sodium carbonate, sodiumhydrogen sulfate, and sodium sulfate, and the hydrophilic compound is atleast one selected from the group consisting of N-t-butyl acrylamidesulfonate, sodium vinyl sulfonate, 2-sodium sulfoethyl methacrylate,sodium sulfonate-containing urethane acrylate, potassium N-t-butylacrylamide sulfonate, and sodium 3-mercapto-1-propane sulfonate.
 3. Thehydrophilic treatment coating composition according to claim 1, whereinthe radical reactive functional group of the hydrophilic compound is atleast one kind that is selected from an acrylamide group, an acryloylgroup, a methacryloyl group, an allyl group, a vinyl group, a styrylgroup, and a mercapto group.
 4. The hydrophilic treatment coatingcomposition according to claim 1, wherein a number-average molecularweight of the hydrophilic compound is 70 to
 500. 5-14. (canceled) 15.The hydrophilic treatment coating composition according to claim 1,wherein the radical polymerization initiator does not include anazo-based compound.
 16. The hydrophilic treatment coating compositionaccording to claim 1, wherein the radical reactive functional group ofthe hydrophilic compound is at least one kind that is selected from anacrylamide group, an acryloyl group, a methacryloyl group, a vinylgroup, a styryl group, and a mercapto group.